Halogen substituted metallocene compounds for olefin polymerization

ABSTRACT

A metallocene compound comprises a transition metal and at least one substituted monocyclic or polycyclic arene ligand bonded to the transition metal, wherein said arene ligand comprises at least one halogen substituent directly bonded to an sp 2  carbon atom at a bondable ring position of an aromatic five-membered ring of said arene ligand.

FIELD

This invention relates to halogen substituted metallocene compounds andtheir use in catalyst systems for olefin polymerization.

BACKGROUND

Various processes and catalysts exist for the homopolymerization orcopolymerization of olefins. For many applications, it is desirable fora polyolefin to have a high weight average molecular weight while havinga relatively narrow molecular weight distribution. A high weight averagemolecular weight, when accompanied by a narrow molecular weightdistribution, provides a polyolefin with high strength properties.

Traditional Ziegler-Natta catalysts systems comprise a transition metalcompound co-catalyzed by an aluminum alkyl and are typically capable ofproducing polyolefins having a high molecular weight, but with a broadmolecular weight distribution:

More recently metallocene catalyst systems have been developed whereinthe transition metal compound has one or more cyclopentadienyl, indenylor fluorenyl ring ligands (typically two). Metallocene catalyst systems,when activated with cocatalysts, such as alumoxane, are effective topolymerize monomers to polyolefins having not only a high weight averagemolecular weight but also a narrow molecular weight distribution.

Particular focus has been directed to metallocenes containingsubstituted, bridged indenyl rings, since these materials areparticularly effective in producing isotactic propylene polymers havinghigh isotacticity and narrow molecular weight distribution. Considerableeffort has been made toward obtaining metallocene produced propylenepolymers having ever-higher molecular weight and melting point, whilemaintaining suitable catalyst activity. Researchers currently believethat there is a direct relationship between the way in which ametallocene is substituted, and the molecular structure of the resultingpolymer. For the substituted, bridged indenyl type metallocenes, it isbelieved that the type and arrangement of substituents on the indenylgroups, as well as the type of bridge connecting the indenyl groups,determines such polymer attributes as molecular weight and meltingpoint. Unfortunately, it is impossible at this time to accuratelycorrelate specific substitution patterns with specific polymerattributes, though minor trends may be identified, from time to time.

For example, U.S. Pat. No. 5,840,644 describes certain metallocenescontaining aryl-substituted indenyl derivatives as ligands, which aresaid to provide propylene polymers having high isotacticity, narrowmolecular weight distribution and very high molecular weight.

Likewise, U.S. Pat. No. 5,936,053 describes certain metallocenecompounds said to be useful for producing high molecular weightpropylene polymers. These metallocenes have a specific hydrocarbonsubstituent at the 2 position and an unsubstituted aryl substituent atthe 4 position, on each indenyl group of the metallocene compound.

In addition to hydrocarbon substituents, it is also known to includehalogen substituents on metallocene compounds. For example, U.S. Pat.No. 3,678,088 discloses polychlorinated metallocenes having formulaeC₅H_(5-m)Cl_(m)MC₅H₅ and (C₅H_(5-n)Cl_(n))₂M wherein M is iron,ruthenium or osmium, m is an integer from 3 to 5, inclusive and n is aninteger from 2 to 5, inclusive. There is no disclosure of thepolychlorinated metallocenes being used as olefin polymerizationcatalysts.

Similarly, chlorinated metallocenes including (CpCl)₂TiCl₂,(CpCl)(Cp)TiCl₂, (CpCl)₂TiClMe, and (CpCl)(Cp)TiClMe are disclosed in J.Am. Chem. Soc. 1988, 110, 2406; J. Organometallic Chem. 1988, 358, 161;Organometallics 1985, 4, 688 and Electrochimica Acta, 1995, 40, 473.

Fluorinated bisindenyl metallocenes, particularlybis(4,7-difluoroindenyl)zirconium dichloride andbis(4,7-difluoroindenyl)zirconium dibenzyl, and their use in olefinpolymerization are discussed in Organometallics, 1990, 9, 3098.

Brominated fluorenylcyclopentadienyl metallocenes, particularly(2,7-dibromofluorenyl)(cyclopentadienyl)zirconium dichloride,(2,7-dibromofluorenyl)(cyclopentadienyl)zirconium dimethyl and(2-bromofluorenyl)(cyclopentadienyl)zirconium dichloride, and their usein olefin polymerization are discussed in J. Organometallic Chem., 1995,501, 101.

U.S. Patent Application Publication No. 2002/0193535 discloses a processfor polymerizing propylene in the presence of a Group 3-5 transitionmetal catalyst having two indenoindolyl ligands, wherein the term“indenoindole” is defined to mean an organic compound that has bothindole and indene rings in which the five-membered rings from each arefused. The indenoindole rings can be substituted with a variety ofmoieties, including halogen, and specifically disclosed and exemplifiedis bis(2-chloro-5-phenyl-5,10-dihydroindeno[1,2-b]-indolyl)zirconiumdichloride

U.S. Pat. Nos. 5,504,232, 5,763,542 and 6,087,292 disclose olefinpolymerization catalysts based on bridged halogen substituted indenylsof Groups 4-6, such as Zr and Hf. Particularly exemplified arerac-dimethylsilanediylbis(5(6)-fluoroindenyl)zirconium dichloride (Fmixed in 5 and 6 positions),rac-dimethylsilanediylbis(5-chloroindenyl)zirconium dichloride,rac-dimethylsilanediyl bis(4(7)-fluoroindenyl)zirconium dichloride (Fmixed in 4 and 7 positions), andrac-dimethylsilanediylbis(5,6-dichloroindenyl)zirconium dichloride. Thebridging groups are connected to the indenyl rings at 1-position.

JP1999-080183A discloses halogenated substituents on racemic carbonbridged bis-indenyl Group 4 transition metal complexes. The applicationfocuses on the use of these complexes as pre-catalysts for thecopolymerization of vinyl aromatic monomers (styrene). The onlycomplexes exemplified are isopropylidene-bis(5- or6-fluoroindenyl)zirconium bisdimethylamide, isopropylidene-bis(5- or6-fluoroindenyl)zirconium dichloride,isopropylidene-bis(5-chloroindenyl) zirconium bisdimethylamide, andisopropylidene-bis(5-chloroindenyl)zirconium dichloride. The applicationgives preference to F>Cl>Br.

JP1995-216011A discloses olefin polymerization catalysts comprisingbridged bis-indenyl Group 4-6 transition metal complexes, having halogensubstituents either in the 2 or the 7 position on the indene ring.However, the only complexes exemplified are bridged bis-indenylcomplexes having a fluoro- or chloro- substituent at the 7 position anda hydrocarbyl or substituted hydrocarbyl substituent at the 4 position.

U.S. Patent Application Publication No. 2004/0260107, published Dec. 23,2004, discloses a large number of bridged indenyl substitutedcyclopentadienyl complexes of Group 3 to 6 metals and indicates that thecomplexes are useful as olefin polymerization catalysts. Among thecomplexes specifically disclosed, but not synthesized, aredimethylsilanediyl(2-methyl-4-phenyl-7-chloroindenyl)(2-isopropyl-4-phenylindenyl)zirconiumdichloride,dimethylsilanediyl(2-methyl-4-phenyl-7-bromoindenyl)(2-isopropyl-4-phenylindenyl)zirconiumdichloride,dimethylsilanediyl(2-methyl-4-(1-naphthyl)-7-chloroindenyl)(2-isopropyl-4-(1-naphthyl)indenyl)zirconium dichloride,dimethylsilanediyl(2-methyl-4-(1-naphthyl)-7-bromoindenyl)(2-isopropyl-4-(1-naphthyl)indenyl)zirconiumdichloride,dimethylsilanediyl(2-methyl-4-(p-t-butylphenyl)-7-chloroindenyl)(2-isopropyl-4-(p-t-butylphenyl)indenyl)zirconiumdichloride anddimethylsilanediyl(2-methyl-4-(p-t-butylphenyl)-7-bromoindenyl)(2-isopropyl-4-(p-t-butylphenyl)indenyl)zirconiumdichloride. Again, the bridging groups are connected to the indenylrings at 1-position.

It will therefore be seen that the current focus of research intohalogen substituted indenyl and fluorenyl metallocene compounds has beendirected to materials where the halogen substituent is located on thesix-membered ring component(s) of the indenyl and fluorenyl rings.

Since the effects of various substituents and bridging groups on thepolymerization properties of metallocene catalysts is still largely anempirical matter; there is a continued interest in synthesizing andtesting new metallocene structures.

SUMMARY

In its broadest aspect, the invention resides in a metallocene compoundcomprising a transition metal and at least one substituted monocyclic orpolycyclic arene ligand bonded to the transition metal, wherein saidarene ligand comprises at least one halogen substituent directly bondedto an sp² carbon atom at a bondable ring position of an aromaticfive-membered ring of said arene ligand.

In another aspect, the invention resides in a metallocene compoundcomprising a transition metal, a first substituted indenyl ligandpi-bonded to the transition metal, and a second monoanionic ligandbonded to the transition metal, wherein said first ligand comprises atleast one halogen substituent directly bonded to an sp² carbon atom atthe one, two or three position of the indenyl ligand.

In a further aspect, the invention resides in a metallocene compoundcomprising a transition metal, a first substituted fluorenyl ligandpi-bonded to the transition metal, a second monoanionic ligand bonded tothe transition metal, wherein said first ligand comprises at least onehalogen substituent directly bonded to an sp² carbon atom at the nineposition of the fluorenyl ligand.

Preferably, said second monoanionic ligand is a substituted orunsubstituted monocyclic or polycyclic ligand pi-bonded to thetransition metal, and more preferably is a substituted or unsubstitutedmonocyclic or polycyclic arene ligand pi-bonded to the transition metal.In one embodiment, said second monoanionic ligand is a substituted orunsubstituted indenyl ligand. In another embodiment, said secondmonoanionic ligand is a substituted or unsubstituted fluorenyl ligand.

Conveniently, the transition metal is from a Group 3, 4, 5 or 6 of thePeriodic Table of Elements, or a lanthanide metal or an actinide metaland preferably is a Group 4 transition metal selected from titanium,zirconium and hafnium.

Typically, said at least one halogen substituent is a chloro, bromo, oriodo substituent and preferably is a chloro or bromo substituent.

In yet a further aspect, the invention resides in a metallocene compoundrepresented by the formula (1):

wherein

-   M is a Group 3, 4, 5 or 6 transition metal atom, or a lanthanide    metal atom, or actinide metal atom, and preferably is a Group 4    transition metal selected from titanium, zirconium and hafnium;-   E is a substituted polycyclic arene ligand pi-bonded to M and    including at least one halogen substituent directly bonded to an sp²    carbon atom at a bondable ring position of an aromatic five-membered    ring of said arene ligand;-   A is a monanionic ligand bonded to M;-   Y is bonded to A and to any single bondable position of the ring    structure of E, and is a bridging group containing a Group 13, 14,    15, or 16 element, and is present when y is one and absent when y is    zero;-   y is zero or one; and-   each X is a univalent anionic ligand, or two X are joined and bound    to the metal atom to form a metallocycle ring, or two X are joined    to form a chelating ligand, a diene ligand, or an alkylidene ligand.

Preferably, E is a substituted indenyl ligand and said at least onehalogen substituent is connected to the one, two or three position ofthe indenyl ligand, or E is a substituted fluorenyl ligand and said atleast one halogen substituent is connected to the nine position of thefluorenyl ligand.

In one embodiment, A is a substituted or unsubstituted monocyclic orpolycyclic arene ligand pi-bonded to M, such as an indenyl ligand or afluorenyl ligand.

Typically, said at least one halogen substituent is a chloro, bromo, oriodo substituent and preferably is a chloro or bromo substituent.

In yet another aspect, the invention resides in an olefin polymerizationcatalyst system comprising (a) a metallocene compound as describedherein and (b) an activator.

In still yet a further aspect, the invention resides in an olefinpolymerization process comprising contacting at least one olefin withthe olefin polymerization catalyst system described herein.

DEFINITIONS

As used herein, the numbering scheme for the Periodic Table Groups isthe new notation as set out in CHEMICAL AND ENGINEERING NEWS, 63(5), 27(1985). However, For purposes of this invention and the claims theretothe use of the capital letter Y in a formula herein is NOT meant toindicate yttrium.

As used herein, Me is methyl, t-Bu and ^(t)Bu are tertiary butyl, iPrand ^(i)Pr are isopropyl, Cy is cyclohexyl, and Ph is phenyl.

The terms “hydrocarbyl radical,” “hydrocarbyl” and “hydrocarbyl group”are used interchangeably throughout this document. Likewise the terms“group”, “radical”, and “substituent” are also used interchangeably inthis document. For purposes of this disclosure, “hydrocarbyl radical” isdefined to be a radical, which contains hydrogen atoms and up to 100carbon atoms and which may be linear, branched, or cyclic, and whencyclic, aromatic or non-aromatic.

Substituted hydrocarbyl radicals are radicals in which at least onehydrogen atom has been substituted with at least one functional groupsuch as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SiR*₃,GeR*₃, SnR*₃, PbR*₃ and the like or where at least one non-hydrocarbonatom or group has been inserted within the hydrocarbyl radical, such as—O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—, —As(R*)—, ═As—,—Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)₂—, —Ge(R*)₂—, —Sn(R*)₂—, —Pb(R*)₂—and the like, where R* is independently a hydrocarbyl or halocarbylradical, and two or more R* may join together to form a substituted orunsubstituted saturated, partially unsaturated or aromatic cyclic orpolycyclic ring structure.

Halocarbyl radicals are radicals in which one or more hydrocarbylhydrogen atoms have been substituted with at least one halogen (e.g. F,Cl, Br, I) or halogen-containing group (e.g. CF₃).

Substituted halocarbyl radicals are radicals in which at least onehalocarbyl hydrogen or halogen atom has been substituted with at leastone functional group such as NR*₂, OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂,SR*, BR*₂, SiR*₃, GeR*₃, SnR*₃, PbR*₃ and the like or where at least onenon-carbon atom or group has been inserted within the halocarbyl radicalsuch as —O—, —S—, —Se—, —Te—, —N(R*)—, ═N—, —P(R*)—, ═P—, —As(R*)—,═As—, —Sb(R*)—, ═Sb—, —B(R*)—, ═B—, —Si(R*)₂—, —Ge(R*)₂—, —Sn(R*)₂—,—Pb(R*)₂— and the like, where R* is independently a hydrocarbyl orhalocarbyl radical provided that at least one halogen atom remains onthe original halocarbyl radical. Additionally, two or more R* may jointogether to form a substituted or unsubstituted saturated, partiallyunsaturated or aromatic cyclic or polycyclic ring structure.

Silylcarbyl radicals (also called silylcarbyls) are groups in which thesilyl functionality is bonded directly to the indicated atom or atoms.Examples include SiH₃, SiH₂R*, SiHR*₂, SiR*₃, SiH₂(OR*), SiH(OR*)₂,Si(OR*)₃, SiH₂(NR*₂), SiH(NR*₂)₂, Si(NR*₂)₃, and the like where R* isindependently a hydrocarbyl or halocarbyl radical and two or more R* mayjoin together to form a substituted or unsubstituted saturated,partially unsaturated or aromatic cyclic or polycyclic ring structure.

Germylcarbyl radicals (also called germylcarbyls) are groups in whichthe germyl functionality is bonded directly to the indicated atom oratoms. Examples include GeH₃, GeH₂R*, GeHR*₂, GeR*₃, GeH₂(OR*),GeH(OR*)₂, Ge(OR*)₃, GeH₂(NR*₂), GeH(NR*₂)₂, Ge(NR*₂)₃, and the likewhere R* is independently a hydrocarbyl or halocarbyl radical and two ormore R* may join together to form a substituted or unsubstitutedsaturated, partially unsaturated or aromatic cyclic or polycyclic ringstructure.

Polar radicals, functional groups, or polar groups are groups in which aheteroatom functionality is bonded directly to the indicated atom oratoms. They include heteroatoms of Groups 1-17 of the periodic tableeither alone or connected to other elements by covalent or otherinteractions such as ionic, van der Waals forces, or hydrogen bonding.Examples of functional groups include carboxylic acid, acid halide,carboxylic ester, carboxylic salt, carboxylic anhydride, aldehyde andtheir chalcogen (Group 14) analogues, alcohol and phenol, ether,peroxide and hydroperoxide, carboxylic amide, hydrazide and imide,amidine and other nitrogen analogues of amides, nitrile, amine andimine, azo, nitro, other nitrogen compounds, sulfur acids, seleniumacids, thiols, sulfides, sulfoxides, sulfones, sulfonates, phosphines,phosphates, other phosphorus compounds, silanes, boranes, borates,alanes, aluminates. Functional groups may also be taken broadly toinclude organic polymer supports or inorganic support material such asalumina, and silica. Preferred examples of polar groups include NR*₂,OR*, SeR*, TeR*, PR*₂, AsR*₂, SbR*₂, SR*, BR*₂, SnR*₃, PbR*₃ and thelike where R* is independently a hydrocarbyl, substituted hydrocarbyl,halocarbyl or substituted halocarbyl radical as defined above and two R*may join together to form a substituted or unsubstituted saturated,partially unsaturated or aromatic cyclic or polycyclic ring structure.Also preferred are sulfonate radicals, S(═O)₂OR*, where R* is defined asabove. Examples include SO₃Me (mesylate), SO₃(4-tosyl) (tosylate),SO₃CF₃ (triflate), SO₃(n-C₄F₉) (nonaflate) and the like.

In using the terms “substituted or unsubstituted cyclopentadienylligand”, “substituted or unsubstituted indenyl ligand”, “substituted orunsubstituted fluorenyl ligand”, “substituted or unsubstitutedcyclopentanaphthyl ligand”, “substituted or unsubstituted monocyclicarenyl ligand”, “substituted or unsubstituted polycyclic arenyl ligand”,“substituted or unsubstituted monocyclic ligand”, or “substituted orunsubstituted polycyclic ligand”, the substitution to the aforementionedligand is on a bondable ring position, and each occurrence is selectedfrom hydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, germylcarbyl, a halogen radical, or a polargroup.

In some embodiments, the hydrocarbyl radical is independently selectedfrom methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl,heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl,pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl,dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl,heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl,docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl,heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl,pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl,dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl,heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl,docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl,heptacosynyl, octacosynyl, nonacosynyl, triacontynyl, butadienyl,pentadienyl, hexadienyl, heptadienyl, octadienyl, nonadienyl, anddecadienyl. Also included are isomers of saturated, partiallyunsaturated and aromatic cyclic and polycyclic structures wherein theradical may additionally be subjected to the types of substitutionsdescribed above. Examples include phenyl, methylphenyl, dimethylphenyl,ethylphenyl, diethylphenyl, propylphenyl, dipropylphenyl, benzyl,methylbenzyl, naphthyl, anthracenyl, cyclopentyl, cyclopentenyl,cyclohexyl, cyclohexenyl, methylcyclohexyl, cycloheptyl, cycloheptenyl,norbornyl, norbornenyl, adamantyl and the like. For this disclosure,when a radical is listed, it indicates that radical type and all otherradicals formed when that radical type is subjected to the substitutionsdefined above. Alkyl, alkenyl and alkynyl radicals listed include allisomers including where appropriate cyclic isomers, for example, butylincludes n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, andcyclobutyl (and analogous substituted cyclopropyls); pentyl includesn-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,1-ethylpropyl, and neopentyl (and analogous substituted cyclobutyls andcyclopropyls); butenyl includes E and Z forms of 1-butenyl, 2-butenyl,3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyland 2-methyl-2-propenyl (and cyclobutenyls and cyclopropenyls). Cycliccompound having substitutions include all isomer forms, for example,methylphenyl would include ortho-methylphenyl, meta-methylphenyl andpara-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl,2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl,3,4-dimethylphenyl, and 3,5-dimethylphenyl.

For nomenclature purposes, the following numbering schemes are used forcyclopentadienyl, indenyl, fluorenyl, and cyclopentanaphthyl (alsotermed benzindenyl). It should be noted that indenyl can be consideredas cyclopentadienyl fused with a benzene ring. Analogously, fluorenylcan be considered a cyclopentadienyl with two phenyl rings fused ontothe cyclopentadienyl ring. Each structure below is drawn and named as ananion.

A similar numbering and nomenclature scheme is used forheterocyclopentadienyls, heterophenyls, heteropentalenyls,heterocyclopentapentalenyls, heteroindenyls, heterofluorenyls,heterocyclopentanaphthyls, heterocyclopentaindenyls,heterobenzocyclopentaindenyls, and the like, as illustrated below. Eachstructure is drawn and named as an anion.

Non-limiting examples of heterocyclopentadienyls include:

Further non-limiting examples of heterocyclopentadienyls include1,3-diazacyclopentadienyl, 1,3-diphosphacyclopentadienyl,1,3-diarsacyclopentadienyl, 1,3-distibacyclopentadienyl,1,3-diboracyclopentadienyl, 1,3-azaphosphacyclopentadienyl,1,3-azaarsacylcopentadienyl, 1,3-azastibacyclopentadienyl,1,3-azaboracyclopentadienyl, 1,3-arsaphosphacyclopentadienyl,1,3-arsastibacyclopentadienyl, 1,3-arsaboracyclopentadienyl,1,3-boraphosphacyclopentadienyl, 1,3-borastibacylcopentadienyl,1,3-phosphastibacyclopentadienyl, 1,2-diazacyclopentadienyl,1,2-diphosphacyclopentadienyl, 1,2-diarsacyclopentadienyl,1,2-distibacyclopentadienyl, 1,2-diboracyclopentadienyl,1,2-azaphosphacyclopentadienyl, 1,2-azaarsacylcopentadienyl,1,2-azastibacyclopentadienyl, 1,2-azaboracyclopentadienyl,1,2-arsaphosphacyclopentadienyl, 1,2-arsastibacyclopentadienyl,1,2-arsaboracyclopentadienyl, 1,2-boraphosphacyclopentadienyl,1,2-borastibacylcopentadienyl, 1,2-phosphastibacyclopentadienyl,3-dihydrocarbylamino-1,3-azaborollide,2-dihydrocarbylamino-1,2-oxaborollide,2-dihydrocarbylamino-1,2-thiaborollide,3-hydrocarbyloxy-1,3-azaborollide, 2-hydrocarbyloxy-1,2-oxaborollide,2-hydrocarbyloxy-1,2-thiaborollide, 3-hydrocarbyl-1,3-azaborollide,2-hydrocarbyl-1,2-oxaborollide, and 2-hydrocarbyl-1,2-thiaborollide,where hydrocarbyl is a “hydrocarbyl radical” as previously defined.

Non-limiting examples of heterophenyls include:

Further non-limiting examples of heterophenyls include1-dihydrocarbylaminoboratabenzene,4-dihydrocarbylamino-1,4-phosphaboratabenzene,2-dihydrocarbylamino-1,2-azaboratabenzene,1-hydrocarbyloxyboratabenzene,4-hydrocarbyloxy-1,4-phosphaboratabenzene,2-hydrocarbyloxy-1,2-azaboratabenzene, 1-hydrocarbylboratabenzene,4-hydrocarbyl-1,4-phosphaboratabenzene, and2-hydrocarbyl-1,2-azaboratabenzene, where hydrocarbyl is a “hydrocarbylradical” as previously defined.

Non-limiting examples of heteropentalenyls include:

Further non-limiting examples of heteropentalenyls includecyclopenta[b]selenophenyl, cyclopenta[c]selenophenyl,cyclopenta[b]tellurophenyl, cyclopenta[c]tellurophenyl,1-hydrocarbylcyclopenta[b]arsolyl, 2-hydrocarbylcyclopenta[c]arsolyl,1-hydrocarbylcyclopenta[b]stibolyl, 2-hydrocarbylcyclopenta[c]stibolyl,1-hydrocarbylcyclopenta[b]pyrrolyl, 2-hydrocarbylcyclopenta[c]pyrrolyl,1-hydrocarbylcyclopenta[b]phospholyl, and2-hydrocarbylcyclopenta[c]phospholyl, where hydrocarbyl is a“hydrocarbyl radical” as previously defined.

Non-limiting examples of heterocylopentapentalenyls include thefollowing, where Z and Q independently represent the heteroatoms O, S,Se, or Te, or heteroatom groups, NR**, PR**, AsR**, or SbR** where R**is hydrogen, or a hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, silylcarbyl, or germylcarbyl substituent.

Non-limiting examples of heteroindenyls include:

Further non-limiting examples of heteroindenyls includecyclopenta[b]arsinyl, cyclopenta[c]arsinyl, cyclopenta[b]stibinyl,cyclopenta[c]stibinyl, 3-dihydrocarbylamino-1,3-benzothiaborollide,2-dihydrocarbylamino-1,2-benzothiaborollide,3-hydrocarbyloxy-1,3-benzothiaborollide,2-hydrocarbyloxy-1,2-benzothiaborollide,3-hydrocarbyl-1,3-benzothiaborollide, and2-hydrocarbyl-1,2-benzothiaborollide, where hydrocarbyl is a“hydrocarbyl radical” as previously defined.

Non-limiting examples of heterofluorenyls include:

Non-limiting examples of heterocyclopentanaphthyls include:

Further non-limiting examples of heterocyclopentanaphthyls includecyclopenta[g]phosphinolyl, cyclopenta[g]isophosphinolyl,cyclopenta[g]arsinolyl, and cyclopenta[g]isoarsinolyl.

Non-limiting examples of heterocyclopentaindenyls include:

Further non-limiting examples of heterocyclopentaindenyls include1-hydrocarbylcyclopenta[f]phosphindolyl,2-hydrocarbylcyclopenta[f]isophosphindolyl,1-hydrocarbylcyclopenta[f]arsindolyl,2-hydrocarbylcyclopenta[f]isoarsindolyl, indeno[5,6-b]selenophenyl,indeno[5,6-b]tellurophenyl, indeno[5,6-c]selenophenyl,indeno[5,6-c]tellurophenyl, 2-hydrocarbylcyclopenta[f]isoindolyl, and1-hydrocarbylcyclopenta[f]indolyl, where hydrocarbyl is a “hydrocarbylradical” as previously defined.

Non-limiting examples of heterobenzocyclopentaindenyls include:

Further non-limiting examples of heterobenzocyclopentaindenyls include5-hydrocarbylindeno[1,2-b]indolyl and 5-hydrocarbylindeno[2,1-b]indolyl,where hydrocarbyl is a “hydrocarbyl radical” as previously defined.

The term “arene” ligand is used herein to mean an unsaturated cyclichydrocarbyl ligand that can consist of one ring, or two or more fused orcatenated rings.

As used herein, the term “monocyclic ligand” is intended to mean anysubstituted or unsubstituted C₅ to C₁₀₀ monoanionic aromaticfive-membered or six-membered single ring structure composed of ringcarbon atoms, either alone or in combination with one or more ringheteroatoms. In contrast, the term “monocyclic arene ligand” is usedherein to mean a substituted or unsubstituted monoanionic C₅ to C₁₀₀hydrocarbyl ligand that contains an aromatic five-membered singlehydrocarbyl ring structure (also referred to as a cyclopentadienylring).

As used herein, the term “polycyclic ligand” is intended to mean anysubstituted or unsubstituted C₅ to C₁₀₃ monoanionic partiallyunsaturated or aromatic multiple fused ring structure containing atleast one aromatic five-membered ring structure, said ligand composed ofring carbon atoms, either alone or in combination with one or more ringheteroatoms. In contrast, the term “polycyclic arenyl ligand” is usedherein to mean a substituted or unsubstituted monoanionic C₈ to C₁₀₃hydrocarbyl ligand that contains an aromatic five-membered hydrocarbylring (also referred to as a cyclopentadienyl ring) that is fused to oneor two partially unsaturated, or aromatic hydrocarbyl ring structureswhich may be fused to additional saturated, partially unsaturated, oraromatic hydrocarbyl rings.

Monocyclic ligands include substituted or unsubstitutedheterocyclopentadienyls heterophenyls and cyclopentadienyls. Monocyclicarenyl ligands include substituted or unsubstituted cyclopentadienyls.Polycyclic ligands include substituted or unsubstituted, partiallyunsaturated or aromatic heteroindenyls, heteropentalenyls,heterocyclopentapentalenyls, heterofluorenyls,heterocyclopentanaphthyls, heterocyclopentaindenyls,heterobenzocyclopentaindenyls, indenyls, fluorenyls, andcyclopentanaphthyls. Polycyclic arenyl ligands include substituted orunsubstituted, partially unsaturated or aromatic indenyls, fluorenyls,and cyclopentanaphthyls.

Non-limiting examples of polycyclic arene ligands, named also asmonoanionic ligands, include indenyl, 4,5-dihydroindenyl,4,7-dihydroindenyl, 4,5,6,7-tetrahydroindenyl, fluorenyl,1,2-dihydrotetrahydrofluorenyl, 1,4-dihydrotetrahydrofluorenyl,3,4-dihydrotetrahydrofluorenyl, 1,2,3,4-tetrahydrofluorenyl,1,2,5,6-tetrahydrofluorenyl, 1,2,7,8-tetrahydrofluorenyl,3,4,5,6-tetrahydrofluorenyl, 1,4,5,8-tetrahydrofluorenyl,1,2,3,4,5,6,7,8-octahydrofluorenyl, cyclopenta[b]naphthyl,4,4a-dihydrocyclopenta[b]naphthyl, 5,6-dihydrocyclopenta[b]naphthyl,5,8-dihydrocyclopenta[b]naphthyl, 4,9-dihydrocyclopenta[b]naphthyl,4,4a,5,6-tetrahydrocyclopenta[b]naphthyl,4,5,8,9-tetrahydrocyclopenta[b]naphthyl,4,4a,7,8-tetrahydrocyclopenta[b]naphthyl,4,4a,8a,9-tetrahydrocyclopenta[b]naphthyl,5,6,7,8-tetrahydrocyclopenta[b]naphthyl,4,4a,5,8-tetrahydrocyclopenta[b]naphthyl,4,5,6,9-tetrahydrocyclopenta[b]naphthyl,4,6,7,8-tetrahydrocyclopenta[b]naphthyl,4,6,7,9-tetrahydrocyclopenta[b]naphthyl,4,4a,5,9-tetrahydrocyclopenta[b]naphthyl,4,4a,5,6,7,8-hexahydrocyclopenta[b]naphthyl,4,4a,5,6,8a,9-hexahydrocyclopenta[b]naphthyl,4,4a,5,8,8a,9-hexahydrocyclopenta[b]naphthyl,4,5,6,7,8,9-hexahydrocyclopenta[b]naphthyl,4,4a,5,6,7,9-hexahydrocyclopenta[b]naphthyl,4,4a,5,6,7,8,8a,9-octahydrocyclopenta[b]naphthyl, cyclopenta[a]naphthyl,4,5-dihydrocyclopenta[a]naphthyl, 6,7-dihydrocyclopenta[a]naphthyl,8,9-dihydrocyclopenta[a]naphthyl, 5a,9a-dihydrocyclopenta[a]naphthyl,6,9-dihydrocyclopenta[a]naphthyl, 7,9a-dihydrocyclopenta[a]naphthyl,4,9a-dihydrocyclopenta[a]naphthyl, 5a,8-dihydrocyclopenta[a]naphthyl,4,5,5a,9a-tetrahydrocyclopenta[a]naphthyl,4,5,6,7-tetrahydrocyclopenta[a]naphthyl,4,5,8,9-tetrahydrocyclopenta[a]naphthyl,5a,6,7,9a-tetrahydrocyclopenta[a]naphthyl,6,7,8,9-tetrahydrocyclopenta[a]naphthyl,5a,8,9,9a-tetrahydrocyclopenta[a]naphthyl,4,5,7,9a-tetrahydrocyclopenta[a]naphthyl,5a,6,7,9a-tetrahydrocyclopenta[a]naphthyl,7,8,9,9a-tetrahydrocyclopenta[a]naphthyl,4,6,7,9a-tetrahydrocyclopenta[a]naphthyl,4,8,9,9a-tetrahydrocyclopenta[a]naphthyl,4,5,6,9-tetrahydrocyclopenta[a]naphthyl,4,5,5a,8-tetrahydrocyclopenta[a]naphthyl,5a,6,7,8-tetrahydrocyclopenta[a]naphthyl,5a,6,9,9a-tetrahydrocyclopenta[a]naphthyl,5a,6,7,8,9,9a-hexahydrocyclopenta[a]naphthyl,4,6,7,8,9,9a-hexahydrocyclopenta[a]naphthyl,4,5,7,8,9,9a-hexahydrocyclopenta[a]naphthyl,4,5,5a,8,9,9a-hexahydrocyclopenta[a]naphthyl,4,5,5a,6,9,9a-hexahydrocyclopenta[a]naphthyl,4,5,5a,6,7,9a-hexahydrocyclopenta[a]naphthyl,4,5,5a,6,7,8-hexahydrocyclopenta[a]naphthyl,4,5,6,7,8,9-hexahydrocyclopenta[a]naphthyl,4,5,5a,6,7,8,9,9a-hexahydrocyclopenta[a]naphthyl,4,5,5a,6,7,8,9,9a-octahydrocyclopenta[a]naphthyl,5,6-trimethyleneindenyl, 4,5-trimethyleneindenyl,5,6-pentamethyleneindenyl, 4,5-pentamethyleneindenyl,5,6-hexamethyleneindenyl, 4,5-hexamethyleneindenyl,5,6-heptamethyleneindenyl, 4,5-heptamethyleneindenyl,5,6-octamethyleneindenyl, 4,5-octamethyleneindenyl,5,6-nonamethyleneindenyl, 4,5-nonamethyleneindenyl,5,6-decamethyleneindenyl, 4,5-decamethyleneindenyl,5,6-undecamethyleneindenyl, 4,5-undecamethyleneindenyl,5,6-dodecamethyleneindenyl, 4,5-dodecamethyleneindenyl,5,6-tridecamethyleneindenyl, 4,5-tridecamethyleneindenyl,5,6-tetradecamethyleneindenyl, 4,5-tetradecamethyleneindenyl,5,6-pentadecamethyleneindenyl, 4,5-pentadecamethyleneindenyl,5,6-hexadecamethyleneindenyl, 4,5-hexadecamethyleneindenyl,5,6-heptadecamethyleneindenyl, 4,5-heptadecamethyleneindenyl,5,6-octadecamethyleneindenyl, 4,5-octadecamethyleneindenyl,5,6-nonadecamethyleneindenyl, 4,5-nonadecamethyleneindenyl,5,6-eicosamethyleneindenyl, 4,5-eicosamethyleneindenyl,(6Z,8Z,10Z)-cycloocta[e]indenyl, (5Z, 7Z, 9Z)-cycloocta[f]indenyl,(5E,7Z,9E,11Z,13E)-cyclododeca[f]indenyl,(6E,8Z,10E,12Z,14E)-cyclododeca[e]indenyl, benz[a]fluorenyl,benz[b]fluorenyl, benz[c]fluorenyl, naphth[2,3-a]fluorenyl,naphth[2,3-b]fluorenyl, naphth[2,3-c]fluorenyl, naphth[1,2-a]fluorenyl,naphth[1,2-b]fluorenyl, naphth[1,2-c]fluorenyl,2,3-tetramethylenefluorenyl, 1,2-tetramethylenefluorenyl,3,4-tetramethylenefluorenyl, 2,3-trimethylenefluorenyl,1,2-trimethylenefluorenyl, 3,4-trimethylenefluorenyl,2,3-pentamethylenefluorenyl, 1,2-pentamethylenefluorenyl,3,4-pentamethylenefluorenyl, 2,3-hexamethylenefluorenyl,1,2-hexamethylenefluorenyl, 3,4-hexamethylenefluorenyl,2,3-heptamethylenefluorenyl, 1,2-heptamethylenefluorenyl,3,4-heptamethylenefluorenyl, 2,3-octamethylenefluorenyl,1,2-octamethylenefluorenyl, 3,4-octamethylenefluorenyl,2,3-nonamethylenefluorenyl, 1,2-nonamethylenefluorenyl,3,4-nonamethylenefluorenyl, 2,3-decamethylenefluorenyl,1,2-decamethylenefluorenyl, 3,4-decamethylenefluorenyl,2,3-undecamethylenefluorenyl, 1,2-undecamethylenefluorenyl,3,4-undecamethylenefluorenyl, 2,3-dodecamethylenefluorenyl,1,2-dodecamethylenefluorenyl, 3,4-dodecamethylenefluorenyl,2,3-tetramethylene-6,7-tetramethylenefluorenyl,1,2-tetramethylene-7,8-tetramethylenefluorenyl,3,4-tetramethylene-5,6-tetramethylenefluorenyl,bis-benz[2,3;6,7]fluorenyl, bis-benz[2,3;5,6]fluorenyl,bis-benz[1,2;7,8]fluorenyl, bis-benz[1,2;5,6]fluorenyl,bis-benz[1,2;6,7]fluorenyl, bis-benz[1,2;7,8]fluorenyl, andbis-benz[3,4;5,6]fluorenyl,

Partially hydrogenated polycyclic arene ligands retain the numberingscheme of the parent polycyclic arene ligand, namely the numberingschemes defined for indenyl, fluorenyl, cyclopenta[b]naphthyl, andcyclopenta[a]naphthyl ligands.

A “ring carbon atom” is a carbon atom that is part of a cyclic ringstructure. By this definition, an indenyl fragment has nine ring carbonatoms. Whereas the monocyclic and polycyclic arene ligands describedherein generally contain only ring carbon atoms, it is within the scopeof the invention to replace one of more of the ring carbon atoms with aheteroatom, such as a boron atom, a Group 14 atom that is not carbon, aGroup 15 atom, or a Group 16 atom. Preferred heteroatoms include boron,nitrogen, oxygen, phosphorus, and sulfur.

A “bondable ring position” is a ring position that is capable of bearinga substituent or bridging substituent. For example, cyclopenta[b]thienylhas five bondable ring positions (at the carbon atoms) and onenon-bondable ring position (the sulfur atom); cyclopenta[b]pyrrolyl hassix bondable ring positions (at the carbon atoms and at the nitrogenatom).

In the context of this document, “homopolymerization” would produce apolymer made from one monomer. For example, homopolymerization ofpropylene would produce homopolypropylene. Homopolymerization ofethylene would produce homopolyethylene. Likewise, “copolymerization”would produce polymers with more than one monomer type. For example,ethylene copolymers include polymers of ethylene with α-olefins, cyclicolefins and diolefins, vinylaromatic olefins, α-olefinic diolefins,substituted α-olefins, and/or acetylenically unsaturated monomers.

Non-limiting examples of α-olefins include ethylene, propylene,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1-undecene 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene,1-heneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene,1-hexacosene, 1-heptacosene, 1-octacosene, 1-nonacosene, 1-triacontene,4-methyl-1-pentene, 3-methyl-1-pentene, 5-methyl-1-nonene,3,5,5-trimethyl-1-hexene, vinylcyclohexane, and vinylnorbornane.

Non-limiting examples of cyclic olefins and diolefins includecyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene,cyclononene, cyclodecene, norbornene, 4-methylnorbornene,2-methylcyclopentene, 4-methylcyclopentene, vinylcyclohexane,norbornadiene, dicyclopentadiene, 5-ethylidene-2-norbornene,vinylcyclohexene, 5-vinyl-2-norbornene, 1,3-divinylcyclopentane,1,2-divinylcyclohexane, 1,3-divinylcyclohexane, 1,4-divinylcyclohexane,1,5-divinylcyclooctane, 1-allyl-4-vinylcyclohexane,1,4-diallylcyclohexane, 1-allyl-5-vinylcyclooctane, and1,5-diallylcyclooctane.

Non-limiting examples of vinylaromatic olefins include styrene,para-methylstyrene, para-t-butylstyrene, vinylnaphthylene, vinyltoluene,and divinylbenzene.

Non-limiting examples of α-olefinic dienes include 1,4-hexadiene,1,5-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 6-methyl-1,6-heptadiene,1,7-octadiene, 7-methyl-1,7-octadiene, 1,9-decadiene, 1,11-dodecene,1,13-tetradecene and 9-methyl-1,9-decadiene.

Substituted α-olefins (also called functional group containingα-olefins) include those containing at least one non-carbon Group 13 to17 atom bound to a carbon atom of the substituted α-olefin where suchsubstitution if silicon may be adjacent to the double bond or terminalto the double bond, or anywhere in between, and where inclusion ofnon-carbon and non-silicon atoms such as for example B, O, S, Se, Te, N,P, Ge, Sn, Pb, As, F, Cl, Br, or I, are contemplated, where suchnon-carbon or non-silicon moieties are sufficiently far removed from thedouble bond so as not to interfere with the coordination polymerizationreaction with the catalyst and so to retain the generally hydrocarbylcharacteristic. By sufficiently far removed from the double bond weintend that the number of carbon atoms, or the number of carbon andsilicon atoms, separating the double bond and the non-carbon ornon-silicon moiety is preferably 6 or greater, e.g. 7, or 8, or 9, or10, or 11, or 12, or 13, or 14 or more. The number of such carbon atoms,or carbon and silicon atoms, is counted from immediately adjacent to thedouble bond to immediately adjacent to the non-carbon or non-siliconmoiety. Examples include 8,8,8-trifluoro-1-octene, 8-methoxyoct-1-ene,8-methylsulfanyloct-1-ene, 8-dimethylaminooct-1-ene, or combinationsthereof. The use of functional group-containing α-olefins where thefunctional group is closer to the double bond is also within the scopeof embodiments of the invention when such olefins may be incorporated inthe same manner as are their α-olefin analogs. See, “MetalloceneCatalysts and Borane Reagents in The Block/Graft Reactions ofPolyolefins”, T. C. Chung, et al, Polym. Mater. Sci. Eng., v. 73, p. 463(1995), and the masked α-olefin monomers of U.S. Pat. No. 5,153,282.Such monomers permit the preparation of both functional-group containingcopolymers capable of subsequent derivatization, and of functionalmacromers which may be used as graft and block type polymeric segments.Copolymerization can also incorporate α-olefinic macromonomers of up to2000 mer units.

For purposes of this disclosure, the term oligomer refers tocompositions having 2-75 mer units and the term polymer refers tocompositions having 76 or more mer units. A mer is defined as a unit ofan oligomer or polymer that originally corresponded to the monomer(s)used in the oligomerization or polymerization reaction. For example, themer of polyethylene would be ethylene.

The term “catalyst system” is defined to mean a catalystprecursor/activator pair. When “catalyst system” is used to describesuch a pair before activation, it means the unactivated catalyst(precatalyst) together with an activator and, optionally, aco-activator. When it is used to describe such a pair after activation,it means the activated catalyst and the activator or othercharge-balancing moiety.

The transition metal compound may be neutral as in a precatalyst, or acharged species with a counter ion as in an activated catalyst system.

Catalyst precursor is also often referred to as precatalyst, catalyst,catalyst compound, catalyst precursor, transition metal compound ortransition metal complex. These words are used interchangeably.Activator and cocatalyst are also used interchangeably. A scavenger is acompound that is typically added to facilitate oligomerization orpolymerization by scavenging impurities. Some scavengers may also act asactivators and may be referred to as co-activators. A co-activator, thatis not a scavenger, may also be used in conjunction with an activator inorder to form an active catalyst. In some embodiments a co-activator canbe pre-mixed with the transition metal compound to form an alkylatedtransition metal compound, also referred to as an alkylated inventioncompound.

Noncoordinating anion (NCA) is defined to mean an anion either that doesnot coordinate to the catalyst metal cation or that does coordinate tothe metal cation, but only weakly. An NCA coordinates weakly enough thata neutral Lewis base, such as an olefinically or acetylenicallyunsaturated monomer can displace it from the catalyst center. Any metalor metalloid that can form a compatible, weakly coordinating complex maybe used or contained in the noncoordinating anion. Suitable metalsinclude, but are not limited to, aluminum, gold, and platinum. Suitablemetalloids include, but are not limited to, boron, aluminum, phosphorus,and silicon.

A stoichiometric activator can be either neutral or ionic. The termsionic activator, and stoichiometric ionic activator can be usedinterchangeably. Likewise, the terms neutral stoichiometric activator,and Lewis acid activator can be used interchangeably.

DETAILED DESCRIPTION OF THE EMBODIMENTS

The present invention provides metallocene compounds comprising atransition metal and at least one substituted monocyclic or polycyclicarene ligand bonded to the transition metal, wherein said arene ligandcomprises at least one halogen substituent directly bonded to an sp²carbon atom at a bondable ring position of an aromatic five-memberedring of said arene ligand. When combined with a suitable activator,these compounds show activity in the polymerization of olefins, such asethylene and propylene.

In a first embodiment, the invention provides a metallocene compoundcomprising a transition metal, a first substituted indenyl ligandpi-bonded to the transition metal, and a second monoanionic ligandbonded to the transition metal, wherein said first ligand comprises atleast one halogen substituent directly bonded to an sp² carbon atom atthe one, two or three position of the indenyl ligand.

In a second embodiment, the invention provides a metallocene compoundcomprising a transition metal, a first substituted fluorenyl ligandpi-bonded to the transition metal, a second monoanionic ligand bonded tothe transition metal, wherein said first ligand comprises at least onehalogen substituent directly bonded to an sp² carbon atom at the nineposition of the fluorenyl ligand.

Conveniently, in each of said first and second embodiments, thetransition metal is selected from Group 3, 4, 5 or 6 of the PeriodicTable of Elements, or a lanthanide metal or an actinide metal.Preferably, the transition metal is a Group 4 transition metal selectedfrom titanium, zirconium and hafnium.

Conveniently, the second monoanionic ligand in each of said first andsecond embodiments is a substituted or unsubstituted monocyclic orpolycyclic ligand that is pi-bonded to the transition metal and morepreferably is a substituted or unsubstituted monocyclic or polycyclicarene ligand that is pi-bonded to the transition metal. For example, thesecond monoanionic ligand can be a substituted or unsubstituted indenylligand and can be the same as the first ligand.

Alternatively, the second monoanionic ligand is a ligand of the formulaTR″_(t-1-y) where T is heteroatom with a coordination number of threefrom Group 15 or with a coordination number of two from Group 16 of thePeriodic Table of Elements; R″ is selected from a C₃-C₁₀₀ substituted orunsubstituted monocyclic or polycyclic ring structure substituent thatis partially unsaturated, unsaturated or aromatic; or a C₂-C₁₀₀substituted or unsubstituted, unsaturated or partially unsaturated,linear or branched alicyclic hydrocarbyl substituent; or a C₁-C₁₀₀substituted or unsubstituted saturated hydrocarbyl radical; and t is thecoordination number of the heteroatom T so that “t-1-y” indicates thenumber of R″ substituents bonded to T.

When R″ is a C₃-C₁₀₀ substituted or unsubstituted monocyclic orpolycyclic ring structure substituent that is partially unsaturated,unsaturated or aromatic, non-limiting examples of R″ include all isomersof cycloalkenes, and all isomers of hydrocarbyl, substitutedhydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl,germylcarbyl, halogen, or polar group substituted cycloalkanesincluding: cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl,cycloheptenyl, cyclooctenyl, cyclononenyl, cyclodecenyl, cycloundecenyl,cyclododecenyl, cyclotridecenyl, cyclotetradecenyl, cyclopentadecenyl,cyclohexadecenyl, cycloheptadecenyl, cyclooctadecenyl, cyclononadecenyl,cycloeicosenyl, cycloheneicosenyl, cyclodocosenyl, cyclotricosenyl,cyclotetracosenyl, cyclopentacosenyl, cyclohexacosenyl,cycloheptacosenyl, cyclooctacosenyl, cyclononacosenyl,cyclotriacontenyl, cyclobutadienyl, cyclopentadienyl, cyclohexadienyl,cycloheptadienyl, cyclooctadienyl, cyclononadienyl, cyclodecadienyl,cycloundecadienyl, cyclododecadienyl, cyclotridecadienyl,cyclotetradecadienyl, cyclopentadecadienyl, cyclohexadecadienyl,cycloheptadecadienyl, cyclooctadecadienyl, cyclononadecadienyl,cycloeicosadienyl, cycloheneicosadienyl, cyclodocosadienyl,cyclotricosadienyl, cyclotetracosadienyl, cyclopentacosadienyl,cyclohexacosadienyl, cycloheptacosadienyl, cyclooctacosadienyl,cyclononacosadienyl, cyclotriacontadienyl, cyclohexatrienyl,cycloheptatrienyl, cyclooctatrienyl, cyclononatrienyl, cyclodecatrienyl,cycloundecatrienyl, cyclododecatrienyl, cyclotridecatrienyl,cyclotetradecatrienyl, cyclopentadecatrienyl, cyclohexadecatrienyl,cycloheptadecatrienyl, cyclooctadecatrienyl, cyclononadecatrienyl,cycloeicosatrienyl, cycloheneicosatrienyl, cyclodocosatrienyl,cyclotricosatrienyl, cyclotetracosatrienyl, cyclopentacosatrienyl,cyclohexacosatrienyl, cycloheptacosatrienyl, cyclooctacosatrienyl,cyclononacosatrienyl, cyclotriacontatrienyl, cyclooctatetrenyl,cyclononatetrenyl, cyclodecatetrenyl, cycloundecatetrenyl,cyclododecatetrenyl, cyclotridecatetrenyl, cyclotetradecatetrenyl,cyclopentadecatetrenyl, cyclohexadecatetrenyl, cycloheptadecatetrenyl,cyclooctadecatetrenyl, cyclononadecatetrenyl, cycloeicosatetrenyl,cycloheneicosatetrenyl, cyclodocosatetrenyl, cyclotricosatetrenyl,cyclotetracosatetrenyl, cyclopentacosatetrenyl, cyclohexacosatetrenyl,cycloheptacosatetrenyl, cyclooctacosatetrenyl, cyclononacosatetrenyl,cyclotriacontatetrenyl, cyclodecapentaenyl, cycloundecapentaenyl,cyclododecapentaenyl, cyclotridecapentaenyl, cyclotetradecapentaenyl,cyclopentadecapentaenyl, cyclohexadecapentaenyl,cycloheptadecapentaenyl, cyclooctadecapentaenyl, cyclononadecapentaenyl,cycloeicosapentaenyl, cycloheneicosapentaenyl, cyclodocosapentaenyl,cyclotricosapentaenyl, cyclotetracosapentaenyl, cyclopentacosapentaenyl,cyclohexacosapentaenyl, cycloheptacosapentaenyl, cyclooctacosapentaenyl,cyclononacosapentaenyl, cyclotriacontapentaenyl, cyclododecahexaenyl,cyclotridecahexaenyl, cyclotetradecahexaenyl, cyclopentadecahexaenyl,cyclohexadecahexaenyl, cycloheptadecahexaenyl, cyclooctadecahexaenyl,cyclononadecahexaenyl, cycloeicosahexaenyl, cycloheneicosahexaenyl,cyclodocosahexaenyl, cyclotricosahexaenyl, cyclotetracosahexaenyl,cyclopentacosahexaenyl, cyclohexacosahexaenyl, cycloheptacosahexaenyl,cyclooctacosahexaenyl, cyclononacosahexaenyl, cyclotriacontahexaenyl,cyclotetradecaheptaenyl, cyclopentadecaheptaenyl,cyclohexadecaheptaenyl, cycloheptadecaheptaenyl, cyclooctadecaheptaenyl,cyclononadecaheptaenyl, cycloeicosaheptaenyl, cycloheneicosaheptaenyl,cyclodocosaheptaenyl, cyclotricosaheptaenyl, cyclotetracosaheptaenyl,cyclopentacosaheptaenyl, cyclohexacosaheptaenyl,cycloheptacosaheptaenyl, cyclooctacosaheptaenyl, cyclononacosaheptaenyl,cyclotriacontaheptaenyl, cyclohexadecaoctaenyl, cycloheptadecaoctaenyl,cyclooctadecaoctaenyl, cyclononadecaoctaenyl, cycloeicosaoctaenyl,cycloheneicosaoctaenyl, cyclodocosaoctaenyl, cyclotricosaoctaenyl,cyclotetracosaoctaenyl, cyclopentacosaoctaenyl, cyclohexacosaoctaenyl,cycloheptacosaoctaenyl, cyclooctacosaoctaenyl, cyclononacosaoctaenyl,cyclotriacontaoctaenyl, cyclooctadecanonaenyl, cyclononadecanonaenyl,cycloeicosanonaenyl, cycloheneicosanonaenyl, cyclodocosanonaenyl,cyclotricosanonaenyl, cyclotetracosanonaenyl, cyclopentacosanonaenyl,cyclohexacosanonaenyl, cycloheptacosanonaenyl, cyclooctacosanonaenyl,cyclononacosanonaenyl, cyclotriacontanonaenyl, cycloeicosadecaenyl,cycloheneicosadecaenyl, cyclodocosadecaenyl, cyclotricosadecaenyl,cyclotetracosadecaenyl, cyclopentacosadecaenyl, cyclohexacosadecaenyl,cycloheptacosadecaenyl, cyclooctacosadecaenyl, cyclononacosadecaenyl,cyclotriacontadecaenyl, cyclodocosaundecaenyl, cyclotricosaundecaenyl,cyclotetracosaundecaenyl, cyclopentacosaundecaenyl,cyclohexacosaundecaenyl, cycloheptacosaundecaenyl,cyclooctacosaundecaenyl, cyclononacosaundecaenyl,cyclotriacontaundecaenyl, cyclotetracosadodecaenyl,cyclopentacosadodecaenyl, cyclohexacosadodecaenyl,cycloheptacosadodecaenyl, cyclooctacosadodecaenyl,cyclononacosadodecaenyl, cyclotriacontadodecaenyl,cyclohexacosatridecaenyl, cycloheptacosatridecaenyl,cyclooctacosatridecaenyl, cyclononacosatridecaenyl,cyclotriacontatridecaenyl, cyclooctacosatetradecaenyl,cyclononacosatetradecaenyl, cyclotriacontatetradecaenyl,cyclotriacontapentadecaenyl, and the like; all isomers of polycyclicalkenes, and all isomers of hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl, germylcarbyl, halogen,or polar substituted polycyclic alkenes including: norbornenyl,norbornadienyl spiro[4.5]decenyl, spiro[5.7]tridecenyl, and the like;phenyl, and all isomers of hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl, germylcarbyl, halogen,or polar substituted phenyl including: methylphenyl, dimethylphenyl,trimethylphenyl, tetramethylphenyl, ethylphenyl, diethylphenyl,triethylphenyl, tetraethylphenyl, propylphenyl, dipropylphenyl,tripropylphenyl, tetrapropylphenyl, butylphenyl, dibutylphenyl,tributylphenyl, tetrabutylphenyl, hexylphenyl, dihexylphenyl,trihexylphenyl, tetrahexylphenyl, dimethylethylphenyl,dimethylpropylphenyl, dimethylbutylphenyl, dimethylpentylphenyl,dimethylhexylphenyl, diethylmethylphenyl, diethylpropylphenyl,diethylbutylphenyl, diethylpentylphenyl, diethylhexylphenyl,dipropylmethylphenyl, dipropylethylphenyl, dipropylbutylphenyl,dipropylpentylphenyl, dipropylhexylphenyl, dibutylmethylphenyl,dibutylethylphenyl, dibutylpropylphenyl, dibutylpentylphenyl,dibutylhexylphenyl, methylethylphenyl, methylpropylphenyl,methylbutylphenyl, methylpentylphenyl, methylhexylphenyl,ethylpropylphenyl, ethylbutylphenyl, ethylpentylphenyl,ethylhexylphenyl, propylbutylphenyl, propylpentylphenyl,propylhexylphenyl, butylpentylphenyl, butylhexylphenyl, methoxyphenyl,ethoxyphenyl, propoxyphenyl, butoxyphenyl, pentoxyphenyl, hexoxyphenyl,dimethoxyphenyl, phenoxyphenyl, methylmethoxyphenyl,dimethylaminophenyl, dipropylaminophenyl, bis(dimethylamino)phenyl,methyl(dimethylamino)phenyl, trimethylsilylphenyl,trimethylgermylphenyl, trifluoromethylphenyl,bis(trifluoromethyl)phenyl, trifluoromethoxyphenyl and the like; benzyl,and all isomers of hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, silylcarbyl, germylcarbyl, halogen, or polarsubstituted benzyl including: methylbenzyl, dimethylbenzyl,trimethylbenzyl, tetramethylbenzyl, ethylbenzyl, diethylbenzyl,triethylbenzyl, tetraethylbenzyl, propylbenzyl, dipropylbenzyl,tripropylbenzyl, tetrapropylbenzyl, butylbenzyl, dibutylbenzyl,tributylbenzyl, tetrabutylbenzyl, hexylbenzyl, dihexylbenzyl,trihexylbenzyl, tetrahexylbenzyl, dimethylethylbenzyl,dimethylpropylbenzyl, dimethylbutylbenzyl, dimethylpentylbenzyl,dimethylhexylbenzyl, diethylmethylbenzyl, diethylpropylbenzyl,diethylbutylbenzyl, diethylpentylbenzyl, diethylhexylbenzyl,dipropylmethylbenzyl, dipropylethylbenzyl, dipropylbutylbenzyl,dipropylpentylbenzyl, dipropylhexylbenzyl, dibutylmethylbenzyl,dibutylethylbenzyl, dibutylpropylbenzyl, dibutylpentylbenzyl,dibutylhexylbenzyl, methylethylbenzyl, methylpropylbenzyl,methylbutylbenzyl, methylpentylbenzyl, methylhexylbenzyl,ethylpropylbenzyl, ethylbutylbenzyl, ethylpentylbenzyl,ethylhexylbenzyl, propylbutylbenzyl, propylpentylbenzyl,propylhexylbenzyl, butylpentylbenzyl, butylhexylbenzyl, methoxybenzyl,ethoxybenzyl, propoxybenzyl, butoxybenzyl, pentoxybenzyl, hexoxybenzyl,dimethoxybenzyl, phenoxybenzyl, methylmethoxybenzyl,dimethylaminobenzyl, dipropylaminobenzyl, bis(dimethylamino)benzyl,methyl(dimethylamino)benzyl, trifluoromethylbenzyl,bis(trifluoromethylbenzyl), trifluoromethyoxybenzyl,trimethylsilylbenzyl, bis(trimethylsilyl)benzyl, trimethylgermylbenzyland the like; all isomers of polycyclic areneyls, and all isomers ofhydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, germylcarbyl, halogen, or polar substitutedpolycyclic areneyls including: aceanthrylenyl, acenaphthylene,acephenanthrylenyl, anthracenyl, azulenyl, biphenylenyl, chrysenyl,coronenyl, fluoranthenyl, fluorenyl, heptacenyl, heptalenyl,heptaphenyl, hexacenyl, hexaphenyl, as-indacenyl, s-indecenyl, indenyl,naphthalenyl, ovalenyl, pentacenyl, pentalenyl, pentaphenyl, perylenyl,phenalenyl, phenanthrenyl, picenyl, pleiadenyl, pyranthrenyl, pyrenyl,rubicenyl, naphthacenyl, tetraphenylenyl, trinaphthylenyl,triphenylenyl, hexahelicenyl, dibenza[a,h]anthracenyl, indanyl,cholanthrenyl, aceanthrenyl, acephenanthrenyl,1,2,3,4-tetrahydronaphthalenyl, 5,6-didehydroazulenyl,1,4-dihydronaphthalenyl, 5H-cyclobut[e]indenyl,cyclohepta[jk]phenanthrenyl, benz[e]acephenanthrylenyl, octalenyl,pentalene[1,6-cd]pentalenyl, cyclobut[c]indenyl,cyclopenta[l]phenanthrene, naphtha[2,1,8-cde]azulene, fullerenyl and thelike; all isomers of substituted ring assemblies, and all isomers ofhydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, germylcarbyl, halogen, or polar substitutedring assemblies including: biphenyl, terphenyl, binaphthyl,binorbornenyl, phenyl-terphenyl, phenyl-naphthyl, phenyl-anthracenyl,phenyl-phenanthrenyl, bianthracenyl, biphenanthrenyl, and the like; allisomers of bridged monocyclic and polycyclic arenyls, and all isomers ofhydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, germylcarbyl, halogen, or polar substitutedbridged monocyclic and polycyclic arenyls including:1,1-diphenylmethano, 1,2-diphenylethano, 1,2-diphenyletheno,1,2-dinaphthylethano, 1,2-dinaphthyletheno, 1,1-dinaphthylmethano,1,1-dianthracenylmethano, 1,2-dianthracenylethano,1,2-dianthracenyletheno and the like; all isomers of heterocycles, andall isomers of hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, silylcarbyl, germylcarbyl, halogen, or polarsubstituted heterocycles including: acridarsinyl, acridinyl,acridophosphinyl, 1H-acrindolinyl, anthrazinyl, anthyridinyl,arsanthridinyl, arsindolyl, arsindolizinyl, arsinolinyl, arsinolizinyl,benzofuranyl, carbazolyl, β-carbolinyl, chromenyl, thiochromenyl,cinnolinyl, furanyl, imidazolyl, indazolyl, indolyl, indolizinyl,isoarsindolyl, isoarsinolinyl, isobenzofuranyl, isochromenyl,isothiochromenyl, isoindolyl, isophosphindolyl, isophosphinolinyl,isoquinolinyl, isothiazolyl, isoxazolyl, naphthyridinyl, oxazolyl,perimidinyl, phenanthrazinyl, phenanthridinyl, phenanthrolinyl,phenazinyl, phosphanthridinyl, phosphindolyl, phosphindolizinyl,phosphinolizinyl, phthalazinyl, pteridinyl, phthaloperinyl, purinyl,pyranyl, thiopyranal, pyrazinyl, pyrazolyl, pyridazinyl, pyridinyl,pyrindinyl, pyrimidinyl, pyrrolyl, pyrrolizinyl, quinazolinyl,quindolinyl, 1H-quinindolinyl, quinolinyl, quinolizinyl, quinoxalinyl,selenophenyl, thebenidinyl, thiazolyl, thiophenyl, triphenodioxazinyl,triphenodithiazinyl, xanthenyl, chromanyl, thiochromanyl, indolinyl,isochromanyl, isothiochromanyl, isoindolinyl, bipyridyl,pyrido[2,1,6-de]quinolizinyl and the like.

When R″ a C₂-C₁₀₀ substituted, unsaturated or partially unsaturated,linear or branched alicyclic hydrocarbyl substituent, non-limitingexamples of R″ include all isomers of alkenes and all isomers ofhydrocarbyl, substituted hydrocarbyl, halocarbyl, substitutedhalocarbyl, silylcarbyl, germylcarbyl, halogen, or polar groupsubstituted alkenes including: ethenyl, propenyl, butenyl, pentenyl,hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl,tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl,octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl,tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl,octacosenyl, nonacosenyl, triacontenyl, butadienyl, pentadienyl,hexadienyl, heptadienyl, octadienyl, nonadienyl, decadienyl,undecadienyl, dodecadienyl, tridecadienyl, tetradecadienyl,pentadecadienyl, hexadecadienyl, heptadecadienyl, octadecadienyl,nonadecadienyl, eicosadienyl, heneicosadienyl, docosadienyl,tricosadienyl, tetracosadienyl, pentacosadienyl, hexacosadienyl,heptacosadienyl, octacosadienyl, nonacosadienyl, triacontadienyl,hexatrienyl, heptatrienyl, octatrienyl, nonatrienyl, decatrienyl,undecatrienyl, dodecatrienyl, tridecatrienyl, tetradecatrienyl,pentadecatrienyl, hexadecatrienyl, heptadecatrienyl, octadecatrienyl,nonadecatrienyl, eicosatrienyl, heneicosatrienyl, docosatrienyl,tricosatrienyl, tetracosatrienyl, pentacosatrienyl, hexacosatrienyl,heptacosatrienyl, octacosatrienyl, nonacosatrienyl, triacontatrienyl,octatetrenyl, nonatetrenyl, decatetrenyl, undecatetrenyl,dodecatetrenyl, tridecatetrenyl, tetradecatetrenyl, pentadecatetrenyl,hexadecatetrenyl, heptadecatetrenyl, octadecatetrenyl, nonadecatetrenyl,eicosatetrenyl, heneicosatetrenyl, docosatetrenyl, tricosatetrenyl,tetracosatetrenyl, pentacosatetrenyl, hexacosatetrenyl,heptacosatetrenyl, octacosatetrenyl, nonacosatetrenyl,triacontatetrenyl, decapentaenyl, undecapentaenyl, dodecapentaenyl,tridecapentaenyl, tetradecapentaenyl, pentadecapentaenyl,hexadecapentaenyl, heptadecapentaenyl, octadecapentaenyl,nonadecapentaenyl, eicosapentaenyl, heneicosapentaenyl, docosapentaenyl,tricosapentaenyl, tetracosapentaenyl, pentacosapentaenyl,hexacosapentaenyl, heptacosapentaenyl, octacosapentaenyl,nonacosapentaenyl, triacontapentaenyl, dodecahexaenyl, tridecahexaenyl,tetradecahexaenyl, pentadecahexaenyl, hexadecahexaenyl,heptadecahexaenyl, octadecahexaenyl, nonadecahexaenyl, eicosahexaenyl,heneicosahexaenyl, docosahexaenyl, tricosahexaenyl, tetracosahexaenyl,pentacosahexaenyl, hexacosahexaenyl, heptacosahexaenyl,octacosahexaenyl, nonacosahexaenyl, triacontahexaenyl,tetradecaheptaenyl, pentadecaheptaenyl, hexadecaheptaenyl,heptadecaheptaenyl, octadecaheptaenyl, nonadecaheptaenyl,eicosaheptaenyl, heneicosaheptaenyl, docosaheptaenyl, tricosaheptaenyl,tetracosaheptaenyl, pentacosaheptaenyl, hexacosaheptaenyl,heptacosaheptaenyl, octacosaheptaenyl, nonacosaheptaenyl,triacontaheptaenyl, hexadecaoctaenyl, heptadecaoctaenyl,octadecaoctaenyl, nonadecaoctaenyl, eicosaoctaenyl, heneicosaoctaenyl,docosaoctaenyl, tricosaoctaenyl, tetracosaoctaenyl, pentacosaoctaenyl,hexacosaoctaenyl, heptacosaoctaenyl, octacosaoctaenyl, nonacosaoctaenyl,triacontaoctaenyl, octadecanonaenyl, nonadecanonaenyl, eicosanonaenyl,heneicosanonaenyl, docosanonaenyl, tricosanonaenyl, tetracosanonaenyl,pentacosanonaenyl, hexacosanonaenyl, heptacosanonaenyl,octacosanonaenyl, nonacosanonaenyl, triacontanonaenyl, eicosadecaenyl,heneicosadecaenyl, docosadecaenyl, tricosadecaenyl, tetracosadecaenyl,pentacosadecaenyl, hexacosadecaenyl, heptacosadecaenyl,octacosadecaenyl, nonacosadecaenyl, triacontadecaenyl, docosaundecaenyl,tricosaundecaenyl, tetracosaundecaenyl, pentacosaundecaenyl,hexacosaundecaenyl, heptacosaundecaenyl, octacosaundecaenyl,nonacosaundecaenyl, triacontaundecaenyl, tetracosadodecaenyl,pentacosadodecaenyl, hexacosadodecaenyl, heptacosadodecaenyl,octacosadodecaenyl, nonacosadodecaenyl, triacontadodecaenyl,hexacosatridecaenyl, heptacosatridecaenyl, octacosatridecaenyl,nonacosatridecaenyl, triacontatridecaenyl, octacosatetradecaenyl,nonacosatetradecaenyl, triacontatetradecaenyl, triacontapentadecaenyl,cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene,cyclononylidene, cyclodecylidene, cycloundecylidene,cyclododecylidene,and the like.

When R″ is a C₁-C₁₀₀ substituted or unsubstituted saturated hydrocarbylradical, non-limiting examples of R″ include methyl, ethyl, and allisomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl,tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl,nonacosyl, and triacontyl; cyclopropyl, and all isomers of cyclobutyl,cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl, cyclotetradecyl,cyclopentadecyl, cyclohexadecyl, cycloheptadecyl, cyclooctadecyl,cyclononadecyl, cycloeicosyl, cycloheneicosyl, cyclodocosyl,cyclotricosyl, cyclotetracosyl, cyclopentacosyl, cyclohexacosyl,cycloheptacosyl, cyclooctacosyl, cyclononacosyl, and cyclotriacontyl;all isomers of norbornyl, adamantyl, cubanyl, prismanyl, andspiro[4,5]decanyl; pefluoromethyl, perfluoroethyl, and all isomers ofperfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl,perfluoroheptyl, perfluorooctyl, perfluorononyl, perfluorodecyl,perfluoroundecyl, perfluorododecyl, perfluorotridecyl,perfluorotetradecyl, perfluoropentadecyl, perfluorohexadecyl,perfluoroheptadecyl, perfluorooctadecyl, perfluorononadecyl,perfluoroeicosyl, perfluoroheneicosyl, perfluorodocosyl,perfluorotricosyl, perfluorotetracosyl, perfluoropentacosyl,perfluorohexacosyl, perfluoroheptacosyl, perfluorooctacosyl,perfluorononacosyl, and perfluorotriacontyl; fluoromethyl, and allisomers of fluoroethyl, fluoropropyl, fluorobutyl, fluoropentyl,fluorohexyl, fluoroheptyl, fluorooctyl, fluorononyl, fluorodecyl,perfluoroundecyl, fluorododecyl, fluorotridecyl, fluorotetradecyl,fluoropentadecyl, fluorohexadecyl, fluoroheptadecyl, fluorooctadecyl,fluorononadecyl, fluoroeicosyl, fluoroheneicosyl, fluorodocosyl,fluorotricosyl, fluorotetracosyl, fluoropentacosyl, fluorohexacosyl,fluoroheptacosyl, fluorooctacosyl, fluorononacosyl, andfluorotriacontyl; methoxymethyl, ethoxymethyl, and all isomers ofmethoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl,methoxyheptyl, methoxyoctyl, methoxynonyl, methoxydecyl, methoxyundecyl,methoxydodecyl, methoxytridecyl, methoxytetradecyl, methoxypentadecyl,methoxyhexadecyl, methoxyheptadecyl, methoxyoctadecyl, methoxynonadecyl,methoxyeicosyl, methoxyheneicosyl, methoxydocosyl, methoxytricosyl,methoxytetracosyl, methoxypentacosyl, methoxyhexacosyl,methoxyheptacosyl, methoxyoctacosyl, methoxynonacosyl,methoxytriacontyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl,ethoxyhexyl, ethoxyheptyl, ethoxyoctyl, ethoxynonyl, ethoxydecyl,ethoxyundecyl, ethoxydodecyl, ethoxytridecyl, ethoxytetradecyl,ethoxypentadecyl, ethoxyhexadecyl, ethoxyheptadecyl, ethoxyoctadecyl,ethoxynonadecyl, ethoxyeicosyl, ethoxyheneicosyl, ethoxydocosyl,ethoxytricosyl, ethoxytetracosyl, ethoxypentacosyl, ethoxyhexacosyl,ethoxyheptacosyl, ethoxyoctacosyl, ethoxynonacosyl, ethoxytriacontyl,propoxymethyl, propoxyethyl, propoxypropyl, propoxybutyl, propoxypentyl,propoxyhexyl, propoxyheptyl, propoxyoctyl, propoxynonyl, propoxydecyl,propoxyundecyl, propoxydodecyl, propoxytridecyl, propoxytetradecyl,propoxypentadecyl, propoxyhexadecyl, propoxyheptadecyl,propoxyoctadecyl, propoxynonadecyl, propoxyeicosyl, propoxyheneicosyl,propoxydocosyl, propoxytricosyl, propoxytetracosyl, propoxypentacosyl,propoxyhexacosyl, propoxyheptacosyl, propoxyoctacosyl, propoxynonacosyl,propoxytriacontyl, butoxymethyl, butoxyethyl, butoxypropyl, butoxybutyl,butoxypentyl, butoxyhexyl, butoxyheptyl, butoxyoctyl, butoxynonyl,butoxydecyl, butoxyundecyl, butoxydodecyl, butoxytridecyl,butoxytetradecyl, butoxypentadecyl, butoxyhexadecyl, butoxyheptadecyl,butoxyoctadecyl, butoxynonadecyl, butoxyeicosyl, butoxyheneicosyl,butoxydocosyl, butoxytricosyl, butoxytetracosyl, butoxypentacosyl,butoxyhexacosyl, butoxyheptacosyl, butoxyoctacosyl, butoxynonacosyl, andbutoxytriacontyl; dimethylaminomethyl, and all isomers ofdimethylaminoethyl, dimethylaminopropyl, dimethylaminobutyl,dimethylaminopentyl, dimethylaminohexyl, dimethylaminoheptyl,dimethylaminooctyl, dimethylaminononyl, dimethylaminodecyl,dimethylaminoundecyl, dimethylaminododecyl, dimethylaminotridecyl,dimethylaminotetradecyl, dimethylaminopentadecyl,dimethylaminohexadecyl, dimethylaminoheptadecyl, dimethylaminooctadecyl,dimethylaminononadecyl, dimethylaminoeicosyl, dimethylaminoheneicosyl,dimethylaminodocosyl, dimethylaminotricosyl, dimethylaminotetracosyl,dimethylaminopentacosyl, dimethylaminohexacosyl,dimethylaminoheptacosyl, dimethylaminooctacosyl, dimethylaminononacosyl,and dimethylaminotriacontyl; trimethylsilylmethyl, and all isomers oftrimethylsilylethyl, trimethylsilylpropyl, trimethylsilylbutyl,trimethylsilylpentyl, trimethylsilylhexyl, trimethylsilylheptyl,trimethylsilyloctyl, trimethylsilylnonyl, trimethylsilyldecyl,trimethylsilylundecyl, trimethylsilyldodecyl, trimethylsilyltridecyl,trimethylsilyltetradecyl, trimethylsilylpentadecyl,trimethylsilylhexadecyl, trimethylsilylheptadecyl,trimethylsilyloctadecyl, trimethylsilylnonadecyl, trimethylsilyleicosyl,trimethylsilylheneicosyl, trimethylsilyldocosyl, trimethylsilyltricosyl,trimethylsilyltetracosyl, trimethylsilylpentacosyl,trimethylsilylhexacosyl, trimethylsilylheptacosyl,trimethylsilyloctacosyl, trimethylsilylnonacosyl, andtrimethylsilyltriacontyl; trimethylgermylmethyl, and all isomers oftrimethylgermylethyl, trimethylgermylpropyl, trimethylgermylbutyl,trimethylgermylpentyl, trimethylgermylhexyl, trimethylgermytheptyl,trimethylgermyloctyl, trimethylgermylnonyl, trimethylgermyldecyl,trimethylgermylundecyl, trimethylgermyldodecyl, trimethylgermyltridecyl,trimethylgermyltetradecyl, trimethylgermylpentadecyl,trimethylgermylhexadecyl, trimethylgermylheptadecyl,trimethylgermyloctadecyl, trimethylgermylnonadecyl,trimethylgermyleicosyl, trimethylgermylheneicosyl,trimethylgermyldocosyl, trimethylgermyltricosyl,trimethylgermyltetracosyl, trimethylgermylpentacosyl,trimethylgermylhexacosyl, trimethylgermylheptacosyl,trimethylgermyloctacosyl, trimethylgermylnonacosyl, andtrimethylgermyltriacontyl

Preferably, R″ is selected from methyl, ethyl, all propyl isomers, allbutyl isomers, phenyl, benzyl, phenethyl, 1-adamantyl, cyclododecyl,cyclohexyl and norbornyl.

Preferably, the at least one halogen substituent is a chloro, bromo oriodo substituent, and more preferably is a chloro or bromo substituent.

In a third embodiment, the invention provides a metallocene compoundrepresented by the formula (1):

wherein

-   M is a Group 3, 4, 5 or 6 transition metal atom, or a lanthanide    metal atom, or actinide metal atom, and preferably is a Group 4    transition metal selected from titanium, zirconium and hafnium;-   E is a substituted polycyclic arene ligand pi-bonded to M and    including at least one halogen substituent directly bonded to an sp₂    carbon atom at a bondable ring position of an aromatic five-membered    ring of said arene ligand;-   A is a monanionic ligand bonded to M;-   Y is bonded to A and to any single bondable position of the ring    structure of E, and is a bridging group containing a Group 13, 14,    15, or 16 element, and is present when y is one and absent when y is    zero;-   y is zero or one; and-   each X is a univalent anionic ligand, or two X are joined and bound    to the metal atom to form a metallocycle ring, or two X are joined    to form a chelating ligand, a diene ligand, or an alkylidene ligand.

Conveniently, E is a substituted indenyl ligand and said at least onehalogen substituent is connected to the one, two or three position ofthe indenyl ligand. Alternatively, E is a substituted fluorenyl ligandand said at least one halogen substituent is connected to the nineposition of the fluorenyl ligand.

Conveniently, A is a substituted or unsubstituted monocyclic orpolycyclic ligand that is pi-bonded to the transition metal, and morepreferably is a substituted or unsubstituted monocyclic or polycyclicarene ligand that is pi-bonded to the transition metal. For example, thesecond monoanionic ligand can be a substituted or unsubstituted indenylligand and can be the same as the first ligand.

Alternatively, A is a monoanionic ligand of the formula TR″_(t-1-y)where T is heteroatom with a coordination number of three from Group 15or with a coordination number of two from Group 16 of the Periodic Tableof Elements; R″ is, independently, hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl, substitutedsilylcarbyl, germylcarbyl, or substituted germylcarbyl and t is thecoordination number of the heteroatom T so that “t-1-y” indicates thenumber of R″ substituents bonded to T.

Conveniently, Y is a bridging group containing boron or a Group 14, 15or 16 element. Examples of suitable bridging groups include S, O, NR′,PR′, AsR′, SbR′, O—O, S—S, R′N—NR′, R′P—PR′, O—S, O—NR′, O—PR′, S—NR′,S—PR′, RN—PR′, R′₂C, R′₂Si, R′₂Ge, R′₂CCR′₂, R′₂CCR′₂CR′₂,R′₂CCR′₂CR′₂CR′₂, R′C═CR′, R′C═CR′CR′₂, R′₂CCR′═CR′CR₂, R′C═CR′CR′═CR′,R′C═CR═CR′₂CR′₂, R′₂CSiR′₂, R′₂SiSiR′₂, R′₂CSiR′₂R′₂, R′₂SiCR′₂SiR′₂,R′C═CR′SiR′₂, R′₂CGeR′₂, R′₂GeGeR′₂, R′₂CGeR′₂CR′₂, R′₂GeCR′₂GeR′₂,R′₂SiGeR′₂, R′C═CR′GeR′₂, R′B, R′₂C—BR′, R′₂C—BR′—CR′₂, R′₂CCR′₂,R′₂CR′₂C—O—CR′₂CR′₂, R′₂C—CR′₂CR′₂, R′₂C—O—CR′═CR′, R′₂C—S—CR′₂,R′₂CR′₂C—S—CR′₂CR′₂, R′₂C—S—CR′₂CR′₂, R′₂C—S—CR′═CR′, R′₂C—Se—CR′₂,R′₂CR′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR′═CR′, R′₂C—N═CR′,R′₂C—NR′—CR′₂, R′₂C—NR′-CR′₂CR′₂, R′₂C—NR′—CR′═CR′,R′₂CR′₂C—NR′—CR′₂CR′₂, R′₂C—P═CR′, and R′₂C—PR′—CR′₂ where R′ ishydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbylsubstituent and optionally two or more adjacent R′ may join to form asubstituted or unsubstituted, saturated, partially unsaturated oraromatic, cyclic or polycyclic substituent. Preferred examples for thebridging group Y include CH₂, CH₂CH₂, CH(CH₃)₂, SiMe₂, SiPh₂, SiMePh,Si(CH₂)₃, and Si(CH₂)₄, O, S, NMe, NPh, PMe, PPh.

Preferably, the at least one halogen substituent is a chloro, bromo oriodo substituent, and more preferably is a chloro or bromo substituent.

In a fourth embodiment, the invention provides a metallocene compoundrepresented by the formula (2):

wherein

-   M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanide    metal atom, or actinide metal atom, preferably a Group 4 transition    metal atom selected from titanium, zirconium or hafnium;-   R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ are, independently, hydrogen, or a    hydrocarbyl, substituted hydrocarbyl, halogen, halocarbyl,    substituted halocarbyl, silylcarbyl, substituted silylcarbyl,    germylcarbyl, substituted germylcarbyl, or other heteroatom    substituents wherein the heteroatom is bonded directly to a ring    carbon atom of the indenyl ligand and is boron, a Group 14 atom that    is not carbon, a Group 15 atom, or a Group 16 atom, preferably    boron, nitrogen, oxygen, phosphorus, or sulfur, and adjacent R¹, R²,    R³, R⁴, R⁵, R⁶, and R⁷ may be joined together to form a substituted    or unsubstituted, saturated, partially unsaturated, or aromatic    cyclic or polycyclic substituent;-   Y is an optional bridging group that contains a Group 13, 14, 15, or    16 element, and that is bonded to A and to any single bondable    position of the indenyl ligand, and is present when y is one and    absent when y is zero, and when present, Y replaces one of R¹, R²,    R³, R⁴, R⁵, R⁶, and R⁷ in formula (2);-   y is zero or one;-   A is a substituted or unsubstituted cyclopentadienyl ligand, a    substituted or unsubstituted indenyl ligand, or a substituted or    unsubstituted fluorenyl ligand; and-   each X is a univalent anionic ligand, or two X are joined and bound    to the metal atom to form a metallocycle ring, or two X are joined    to form a chelating ligand, a diene ligand, or an alkylidene ligand;-   provided that at least one of R₁, R₂ and R₃ is a halogen    substituent, preferably a chloro, bromo or iodo substituent, and    more preferably is a chloro or bromo substituent.

In a fifth embodiment, the invention provides a metallocene compoundrepresented by the formula (3):

wherein

-   M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanide    metal atom, or actinide metal atom, preferably a Group 4 transition    metal atom selected from titanium, zirconium or hafnium;-   R^(1′), R^(2′), R^(3′), R^(4′), R^(5′), R^(6′), R^(7′) and R^(8′)    are, independently, hydrogen, or a hydrocarbyl, substituted    hydrocarbyl, halogen, halocarbyl, substituted halocarbyl,    silylcarbyl, substituted silylcarbyl, germylcarbyl, substituted    germylcarbyl, or other heteroatom substituents wherein the    heteroatom is bonded directly to a ring carbon atom of the fluorenyl    ligand and is boron, a Group 14 atom that is not carbon, a Group 15    atom, or a Group 16 atom, preferably boron, nitrogen, oxygen,    phosphorus, or sulfur, and adjacent R^(1′), R^(2′), R^(3′), R^(4′),    R^(5′), R^(6′), R^(7′) and R^(8′) may be joined together to form a    substituted or unsubstituted, saturated, partially unsaturated, or    aromatic cyclic or polycyclic substituent;-   R⁹′ is a halogen substituent, preferably a chloro, bromo or iodo    substituent, and more preferably is a chloro or bromo substituent;-   Y is an optional bridging group that contains a Group 13, 14, 15, or    16 element, and that is bonded to A and to any single bondable    position of the fluorenyl ligand, and is present when y is one and    absent when y is zero, and when present, Y replaces one of R^(1′),    R^(2′), R^(3′), R^(4′), R^(5′), R^(6′), R^(7′) and R^(8′) in formula    (3);-   y is zero or one;-   A is a substituted or unsubstituted cyclopentadienyl ligand, a    substituted or unsubstituted indenyl ligand, or a substituted or    unsubstituted fluorenyl ligand; and-   each X is a univalent anionic ligand, or two X are joined and bound    to the metal atom to form a metallocycle ring, or two X are joined    to form a chelating ligand, a diene ligand, or an alkylidene ligand.

Conveniently, Y in each of formulae (2) and (3) is a bridging groupcontaining boron or a Group 14, 15 or 16 element. Examples of suitablebridging groups include S, O, NR′, PR′, AsR′, SbR′, O—O, S—S, R′N—NR′,R′P—PR′, O—S, O—NR′, O—PR′, S—NR′, S—PR′, R′N—PR′, R′₂C, R′₂Si, R′₂Ge,R′₂CCR′₂, R′₂CCR′₂CR′₂, R′₂CCR′₂CR′₂CR′₂, R′C═CR′, R′C═CR′CR′₂,R′₂CCR′═CR′CR′₂, R′C═CR′CR′═CR′, R′C═CR′CR′₂CR′₂, R′₂CSiR′₂, R′₂SiSiR′₂,R′₂CSiR′₂CR′₂, R′₂SiCR′₂SiR′₂, R′C═CR′SiR′₂, R′₂CGeR′₂, R′₂GeGeR′₂,R′₂CGeR′₂CR′₂, R′₂GeCR′₂GeR′₂, R′₂SiGeR′₂, R′C═CR′GeR′₂, R′B, R′₂C—BR′,R′₂C—BR′—CR′₂, R′₂C—O—CR′₂, R′₂CR′₂C—O—CR′₂CR′₂, R′₂C—O—CR′₂CR′₂,R′₂C—O—CR′═CR′, R′₂C—S—CR′₂, R′₂CR′₂C—S—CR′₂CR′₂, R′₂C—S—CR′₂CR′₂,R′₂C—S—CR′═CR′, R′₂C—Se—CR′₂, R′₂CR′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR′₂CR′₂,R′₂C—Se—CR′═CR′, R′₂C—N═CR′, R′₂C—NR′—CR′₂, R′₂C—NR′—CR′₂CR′₂,R′₂C—NR′—CR′═CR′, R′₂CR′₂C—NR′—CR′₂CR′₂, R′₂C—P═CR′, and R′₂C—PR′—CR′₂where R′ is hydrogen or a C₁-C₂₀ containing hydrocarbyl, substitutedhydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl orgermylcarbyl substituent and optionally two or more adjacent R′ may jointo form a substituted or unsubstituted, saturated, partially unsaturatedor aromatic, cyclic or polycyclic substituent. Preferred examples forthe bridging group Y include CH₂, CH₂CH₂, CH(CH₃)₂, SiMe₂, SiPh₂,SiMePh, Si(CH₂)₃, and Si(CH₂)₄, O, S, NMe, NPh, PMe, PPh.

Examples of metallocene compounds according to the present inventioninclude:

-   (pentamethylcyclopentadienyl)(2-bromoindenyl)zirconium dichloride,-   (pentamethylcyclopentadienyl)(2-bromo-4,7-dimethylindenyl)zirconium    dichloride,-   (cyclopentadienyl)(2-bromoindenyl)zirconium dichloride,-   (cyclopentadienyl)(3-bromoindenyl)zirconium dichloride,-   (cyclopentadienyl)(2-chloroindenyl)zirconium dichloride,-   (2-bromoindenyl)zirconium trichloride,-   (3-bromo-2-dimethylamino-1,2-thiaborollide)zirconium trichloride,-   (2-bromoindenyl)zirconium trichloride,-   (2-bromo-4,7-dimethylindenyl)zirconium trichloride,-   (3-bromoindenyl)zirconium trichloride,-   (2-chloroindenyl)zirconium trichloride,-   dimethylsilanediyl(2-bromoinden-1-yl)(N-tert-butylamido)zirconium    dibromide,-   dimethylsilanediyl(2-bromoinden-1-yl)(N-tert-butylamido)zirconium    diiodide,-   dimethylsilanediyl(2-bromoinden-1-yl)(N-tert-butylamido)zirconium    difluoride,-   dimethylsilanediyl(2-bromoinden-1-yl)(N-tert-butylamido)zirconium    dihydride,-   dimethylsilanediyl(2-bromoinden-1-yl)(N-tert-butylamido)dimethylzirconium,-   dimethylsilanediyl(2-bromoinden-1-yl)(N-tert-butylamido)dibenzylzirconium,-   dimethylsilanediyl(2-bromoinden-1-yl)(N-tert-butylamido)diphenylzirconium,-   dimethylsilanediyl(2-bromoinden-1-yl)(N-tert-butylamido)dimethoxyzirconium,-   dimethylsilanediyl(2-bromoinden-1-yl)(N-tert-butylamido)bis(dimethylamido)    zirconium,-   dimethylsilanediyl(2-bromoinden-1-yl)(N-tert-butylamido)zirconium    dichloride,-   dimethylsilanediyl(2-bromo-4,6-dimethylindeno[5,6-b]thien-7-yl)(N-tert-butylamido)zirconium    dichloride,-   4,N′-dimethylsilanediyl(3-bromo-2-dimethylamino-1,2-thiaborollide)(tert-butylamido)zirconium    dichloride,-   dimethylsilanediyl(2-bromoinden-1-yl)(N-tert-butylamido)zirconium    dichloride,-   dimethylsilanediyl(2-bromo-4,7-dimethylinden-1-yl)(N-tert-butylamido)zirconium    dichloride,-   dimethylsilanediyl(3-bromoinden-1-yl)(N-tert-butylamido)zirconium    dichloride,-   dimethylsilanediyl(2-chloroinden-1-yl)(N-tert-butylamido)zirconium    dichloride,-   bis(2-bromoinden-1-yl)zirconium dichloride,-   bis(3-bromoinden-1-yl)zirconium dichloride,-   bis(2-chloroinden-1-yl)zirconium dichloride,-   rac-dimethylsilanediyl-bis(2-bromoinden-1-yl)zirconium dichloride,-   rac-dimethylsilanediyl-bis(3-bromoinden-1-yl)zirconium dichloride,-   rac-dimethylsilanediyl-bis(2-chloroinden-1-yl)zirconium dichloride,-   4,4′-sulfandiyl-bis(3-bromoindenyl)zirconium dichloride,-   4,4′-sulfandiyl-bis(2-bromoindenyl)zirconium dichloride,-   4,4′-sulfandiyl-bis(1-bromoindenyl)zirconium dichloride,-   4,4′-sulfandiyl-(3-bromoindenyl)(1-phenylindenyl)zirconium    dichloride,-   4,4′-sulfandiyl-(2-bromoindenyl)(1-phenylindenyl)zirconium    dichloride,-   4,4′-sulfandiyl-(1-bromoindenyl)(1-phenylindenyl)zirconium    dichloride,-   4,1′-sulfandiyl-(indenyl)(2-bromoindenyl)zirconium dichloride,-   4,1′-sulfandiyl-(indenyl)(2-chloroindenyl)zirconium dichloride,-   4,1′-sulfandiyl-(indenyl)(2-iodoindenyl)zirconium dichloride,-   4,1′-phenylphosphindiyl-(indenyl)(2-bromoindenyl)zirconium    dichloride,-   4,1′-phenylphosphindiyl-(indenyl)(2-chloroindenyl)zirconium    dichloride,-   4,1′-phenylphosphindiyl-(indenyl)(2-iodoindenyl)zirconium    dichloride,-   5,5′-sulfandiyl-bis(3-bromoindenyl)zirconium dichloride,-   5,5′-sulfandiyl-bis(2-bromoindenyl)zirconium dichloride,-   5,5′-sulfandiyl-bis(1-bromoindenyl)zirconium dichloride,-   5,5′-sulfandiyl-(3-bromoindenyl)(1-phenylindenyl)zirconium    dichloride,-   5,5′-sulfandiyl-(2-bromoindenyl)(1-phenylindenyl)zirconium    dichloride,-   5,5′-sulfandiyl-(1-bromoindenyl)(1-phenylindenyl)zirconium    dichloride,-   4,5′-sulfandiyl-bis(3-bromoindenyl)zirconium dichloride,-   4,5′-sulfandiyl-bis(2-bromoindenyl)zirconium dichloride,-   4,5′-sulfandiyl-bis(1-bromoindenyl)zirconium dichloride,-   4,5′-sulfandiyl-(3-bromoindenyl)(1-phenylindenyl)zirconium    dichloride,-   4,5′-sulfandiyl-(2-bromoindenyl)(1-phenylindenyl)zirconium    dichloride,-   4,5′-sulfandiyl-(1-bromoindenyl)(1-phenylindenyl)zirconium    dichloride, and-   the hafnium and titanium analogs of the examples above.    Halogenated Metallocene Synthesis

There are two general synthetic methods for the preparation of metalcomplexes of formula (1). The first method involves a transmetallationreaction between a metal halide (MX_(n)) and either a salt ornon-transition metal derivative of the ligand HE-Y_(y)-AH. Preferablemetal halides include TiCl₄, TiCl₃, ZrCl₄, ZrBr₄, ZrI₄, HfCl₄, LnCl₃,LnBr₃, LnI₃ (where Ln is Sc, Y, La, or lanthanide group metal), VCl₃,NbCl₅, TaCl₅, CrCl₃, MoCl₅, WCl₆, and the like. Preferable salts(M′J_(p) salts) of halo-substituted monocyclic or polycyclic arenesinclude Li, Na, K, Tl, and Mg salts, and the like. Preferablenon-transition metal derivatives of halo-substituted monocyclic orpolycyclic arenes include Si and Sn derivatives, and the like (Qderivatives). Two general examples of this first synthetic method areshown below.

The following two representative examples further illustrate thismethod.

The second general procedure involves metallation of the compounds ofthe following general formula HE-Yy-AH by the respective transitionmetal derivatives, as shown below.

The following representative example illustrates this method.

Activators and Catalyst Activation

The halogenated metallocene compounds of the invention are useful ascatalyst precursors and, when activated with conventional activators,such as methyl alumoxane, form active catalysts for the polymerizationor oligomerization of olefins. Activators that may be used includealumoxanes such as methyl alumoxane, modified methyl alumoxane, ethylalumoxane, iso-butyl alumoxane and the like; Lewis acid activatorsinclude triphenyl boron, tris-perfluorophenyl-boron,tris-perfluorophenyl aluminum and the like; Ionic activators includedimethylanilinium tetrakis perfluorophenyl borate, triphenyl carboniumtetrakis perfluorophenyl borate, dimethylanilinium tetrakisperfluorophenyl aluminate, and the like.

A co-activator is a compound capable of alkylating the transition metalcomplex, such that when used in combination with an activator, an activecatalyst is formed. Co-activators include alumoxanes such as methylalumoxane, modified alumoxanes such as modified methyl alumoxane, andaluminum alkyls such as trimethyl aluminum, tri-isobutyl aluminum,triethyl aluminum, and tri-isopropyl aluminum. Co-activators aretypically only used in combination with Lewis acid activators and ionicactivators when the pre-catalyst is not a dihydrocarbyl or dihydridecomplex.

The alumoxane component useful as an activator typically is anoligomeric aluminum compound represented by the general formula(R^(x)—Al—O)_(n), which is a cyclic compound, orR^(x)(R^(x)—Al—O)_(n)AlR^(x) ₂, which is a linear compound. In thegeneral alumoxane formula, R^(x) is independently a C₁-C₂₀ alkylradical, for example, methyl, ethyl, propyl, butyl, pentyl, isomersthereof, and the like, and “n” is an integer from 1-50. Most preferably,R^(x) is methyl and “n” is at least 4. Methyl alumoxane and modifiedmethyl alumoxanes are most preferred. For further descriptions see, EP 0279 586, EP 0 594 218, EP 0 561 476, WO94/10180 and U.S. Pat. Nos.4,665,208, 4,874,734, 4,908,463, 4,924,018, 4,952,540, 4,968,827,5,041,584, 5,091,352, 5,103,031, 5,157,137, 5,204,419, 5,206,199,5,235,081, 5,248,801, 5,329,032, 5,391,793, and 5,416,229.

When an alumoxane or modified alumoxane is used, thecatalyst-precursor-to-activator molar ratio is from about 1:3000 to10:1; alternatively, 1:2000 to 10:1; alternatively 1:1000 to 10:1;alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1; alternatively1:200 to 1:1; alternatively 1:100 to 1:1; alternatively 1:50 to 1:1;alternatively 1:10 to 1:1. When the activator is an alumoxane (modifiedor unmodified), some embodiments select the maximum amount of activatorat a 5000-fold molar excess over the catalyst precursor (per metalcatalytic site). The preferred minimum activator to catalyst precursorratio is 1:1 molar ratio.

Ionic activators (at times used in combination with a co-activator) maybe used in the practice of this invention. Preferably, discrete ionicactivators such as [Me₂PhNH][B(C₆F₅)₄], [Ph₃C][B(C₆F₅)₄],[Me₂PhNH][B((C₆H₃-3,5-(CF₃)₂))₄], [Ph₃C][B((C₆H₃-3,5-(CF₃)₂))₄],[NH₄][B(C₆H₅)₄] or Lewis acidic activators such as B(C₆F₅)₃ or B(C₆H₅)₃can be used. Preferred co-activators, when used, are alumoxanes such asmethyl alumoxane, modified alumoxanes such as modified methyl alumoxane,and aluminum alkyls such as tri-isobutyl aluminum, and trimethylaluminum.

It is within the scope of this invention to use an ionizing orstoichiometric activator, neutral or ionic, such as tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate, a trisperfluorophenyl boron metalloidprecursor or a trisperfluoronaphthyl boron metalloid precursor,polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Pat.No. 5,942,459) or combination thereof.

Examples of neutral stoichiometric activators include tri-substitutedboron, tellurium, aluminum, gallium and indium or mixtures thereof. Thethree substituent groups are each independently selected from alkyls,alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy andhalides. Preferably, the three groups are independently selected fromhalogen, mono or multicyclic (including halosubstituted) aryls, alkyls,and alkenyl compounds and mixtures thereof, preferred are alkenyl groupshaving 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms,alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20carbon atoms (including substituted aryls). More preferably, the threegroups are alkyls having 1 to 4 carbon groups, phenyl, naphthyl ormixtures thereof. Even more preferably, the three groups arehalogenated, preferably fluorinated, aryl groups. Most preferably, theneutral stoichiometric activator is trisperfluorophenyl boron ortrisperfluoronaphthyl boron.

Ionic stoichiometric activator compounds may contain an active proton,or some other cation associated with, but not coordinated to, or onlyloosely coordinated to, the remaining ion of the ionizing compound. Suchcompounds and the like are described in European publications EP-A-0 570982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 andEP-A-0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741,5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patentapplication Ser. No. 08/285,380, filed Aug. 3, 1994, all of which areherein fully incorporated by reference.

Ionic catalysts can be prepared by reacting a transition metal compoundwith an activator, such as B(C₆F₆)₃, which upon reaction with thehydrolyzable ligand (X′) of the transition metal compound forms ananion, such as ([B(C₆F₅)₃(X′)]⁻), which stabilizes the cationictransition metal species generated by the reaction. The catalysts canbe, and preferably are, prepared with activator components that areionic compounds or compositions. However preparation of activatorsutilizing neutral compounds is also contemplated by this invention.

Compounds useful as an activator component in the preparation of theionic catalyst systems used in the process of this invention comprise acation, which is preferably a Bronsted acid capable of donating aproton, and a compatible non-coordinating anion which anion isrelatively large (bulky), capable of stabilizing the active catalystspecies which is formed when the two compounds are combined and saidanion will be sufficiently labile to be displaced by olefinic diolefinicand acetylenically unsaturated substrates or other neutral Lewis basessuch as ethers, nitrites and the like. Two classes of compatiblenon-coordinating anions have been disclosed in EPA 277,003 and EPA277,004 published 1988: 1) anionic coordination complexes comprising aplurality of lipophilic radicals covalently coordinated to and shieldinga central charge-bearing metal or metalloid core, and 2) anionscomprising a plurality of boron atoms such as carboranes,metallacarboranes and boranes.

In a preferred embodiment, the stoichiometric activators include acation and an anion component, and may be represented by the followingformula:(L**-H)_(d) ⁺(A^(d−))wherein L** is an neutral Lewis base;

-   H is hydrogen;-   (L**-H)⁺ is a Bronsted acid-   A^(d−) is a non-coordinating anion having the charge d−-   d is an integer from 1 to 3.

The cation component, (L**-H)_(d) ⁺ may include Bronsted acids such asprotons or protonated Lewis bases or reducible Lewis acids capable ofprotonating or abstracting a moiety, such as an alkyl or aryl, from theprecatalyst after alkylation.

The activating cation (L**-H)_(d) ⁺ may be a Bronsted acid, capable ofdonating a proton to the alkylated transition metal catalytic precursorresulting in a transition metal cation, including ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof, preferably ammoniums ofmethylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline,methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine,triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such asdimethyl ether, diethyl ether, tetrahydrofuran and dioxane, sulfoniumsfrom thioethers, such as diethyl thioethers and tetrahydrothiophene, andmixtures thereof. The activating cation (L**-H)_(d) ⁺ may also be amoiety such as silver, tropylium, carbeniums, ferroceniums and mixtures,preferably carboniums and ferroceniums; most preferably triphenylcarbonium.

The anion component A^(d−) include those having the formula[M^(k+)Q_(n)]^(d−) wherein k is an integer from 1 to 3; n is an integerfrom 2-6; n−k=d; M is an element selected from Group 13 of the PeriodicTable of the Elements, preferably boron or aluminum, and Q isindependently a hydride, bridged or unbridged dialkylamido, halide,alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl,substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Qhaving up to 20 carbon atoms with the proviso that in not more than oneoccurrence is Q a halide. Preferably, each Q is a fluorinatedhydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q isa fluorinated aryl group, and most preferably each Q is a pentafluorylaryl group. Examples of suitable Ad- also include diboron compounds asdisclosed in U.S. Pat. No. 5,447,895, which is fully incorporated hereinby reference.

Illustrative, but not limiting examples of boron compounds which may beused as an activating cocatalyst in combination with a co-activator inthe preparation of the improved catalysts of this invention aretri-substituted ammonium salts such as:

-   trimethylammonium tetraphenylborate,-   triethylammonium tetraphenylborate,-   tripropylammonium tetraphenylborate,-   tri(n-butyl)ammonium tetraphenylborate,-   tri(tert-butyl)ammonium tetraphenylborate,-   N,N-dimethylanilinium tetraphenylborate,-   N,N-diethylanilinium tetraphenylborate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetraphenylborate,-   trimethylammonium tetrakis(pentafluorophenyl)borate,-   triethylammonium tetrakis(pentafluorophenyl)borate,-   tripropylammonium tetrakis(pentafluorophenyl)borate,-   tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,-   tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,-   N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(pentafluorophenyl)borate,-   trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   dimethyl(tert-butyl)ammonium    tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   trimethylammonium tetrakis(perfluoronaphthyl)borate,-   triethylammonium tetrakis(perfluoronaphthyl)borate,-   tripropylammonium tetrakis(perfluoronaphthyl)borate,-   tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate,-   tri(tert-butyl)ammonium tetrakis(perfluoronaphthyl)borate,-   N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,-   N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate,-   trimethylammonium tetrakis(perfluorobiphenyl)borate,-   triethylammonium tetrakis(perfluorobiphenyl)borate,-   tripropylammonium tetrakis(perfluorobiphenyl)borate,-   tri(n-butyl)ammonium tetrakis(perfluorobiphenyl)borate,-   tri(tert-butyl)ammonium tetrakis(perfluorobiphenyl)borate,-   N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,-   N,N-diethylanilinium tetrakis(perfluorobiphenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluorobiphenyl)borate,-   trimethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triethylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tripropylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tri(n-butyl)ammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   tri(tert-butyl)ammonium    tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-dimethylanilinium    tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-diethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,    and dialkyl ammonium salts such as:-   di-(iso-propyl)ammonium tetrakis(pentafluorophenyl)borate, and-   dicyclohexylammonium tetrakis(pentafluorophenyl)borate;    and other salts such as:-   tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl)borate,-   tri(2,6-dimethylphenyl)phosphonium    tetrakis(pentafluorophenyl)borate,-   tropillium tetraphenylborate,-   triphenylcarbenium tetraphenylborate,-   triphenylphosphonium tetraphenylborate,-   triethylsilylium tetraphenylborate,-   benzene(diazonium)tetraphenylborate,-   tropillium tetrakis(pentafluorophenyl)borate,-   triphenylcarbenium tetrakis(pentafluorophenyl)borate,-   triphenylphosphonium tetrakis(pentafluorophenyl)borate,-   triethylsilylium tetrakis(pentafluorophenyl)borate,-   benzene(diazonium)tetrakis(pentafluorophenyl)borate,-   tropillium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triphenylphosphonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   triethylsilylium tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   benzene(diazonium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate,-   tropillium tetrakis(perfluoronaphthyl)borate,-   triphenylcarbenium tetrakis(perfluoronaphthyl)borate,-   triphenylphosphonium tetrakis(perfluoronaphthyl)borate,-   triethylsilylium tetrakis(perfluoronaphthyl)borate,-   benzene(diazonium)tetrakis(perfluoronaphthyl)borate,-   tropillium tetrakis(perfluorobiphenyl)borate,-   triphenylcarbenium tetrakis(perfluorobiphenyl)borate,-   triphenylphosphonium tetrakis(perfluorobiphenyl)borate,-   triethylsilylium tetrakis(perfluorobiphenyl)borate,-   benzene(diazonium)tetrakis(perfluorobiphenyl)borate,-   tropillium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triphenylphosphonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,-   triethylsilylium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, and-   benzene(diazonium) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

Most preferably, the ionic stoichiometric activator (L**-H)_(d)⁺(A^(d−)) is N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbeniumtetra(perfluorophenyl)borate.

In a preferred embodiment, the activator is trispentafluorophenylborane.

Invention catalyst precursors can also be activated with cocatalysts oractivators that comprise non-coordinating anions containingmetalloid-free cyclopentadienide ions. These are described in U.S.Patent Publication 2002/0058765 A1, published on 16 May 2002, and forthe instant invention, require the addition of a co-activator to thecatalyst pre-cursor.

The term “non-coordinating anion” (NCA) means an anion that does notcoordinate to the catalyst metal cation or that does coordinate to themetal cation, but only weakly. An NCA coordinates weakly enough that aneutral Lewis base, such as an olefinically or acetylenicallyunsaturated monomer can displace it from the catalyst center.“Compatible” non-coordinating anions are those which are not degraded toneutrality when the initially formed complex decomposes. Further, theanion will not transfer an anionic substituent or fragment to the cationso as to cause it to form a neutral transition metal compound and aneutral by-product from the anion. Non-coordinating anions useful inaccordance with this invention are those that are compatible, stabilizethe transition metal complex cation in the sense of balancing its ioniccharge at +1, yet retain sufficient lability to permit displacement byan ethylenically or acetylenically unsaturated monomer duringpolymerization. These types of cocatalysts sometimes use scavengers suchas but not limited to tri-iso-butyl aluminum, tri-n-octyl aluminum,tri-n-hexyl aluminum, triethylaluminum or trimethylaluminum.

Invention process also can employ cocatalyst compounds or activatorcompounds that are initially neutral Lewis acids but form a cationicmetal complex and a noncoordinating anion, or a zwitterionic complexupon reaction with the alkylated transition metal compounds. Thealkylated invention compound is formed from the reaction of the catalystpre-cursor and the co-activator. For example,tris(pentafluorophenyl)boron or aluminum act to abstract a hydrocarbylligand to yield an invention cationic transition metal complex andstabilizing noncoordinating anion, see EP-A-0 427 697 and EP-A-0 520 732for illustrations of analogous Group-4 metallocene compounds. Also, seethe methods and compounds of EP-A-0 495 375. For formation ofzwitterionic complexes using analogous Group 4 compounds, see U.S. Pat.Nos. 5,624,878; 5,486,632; and 5,527,929.

Additional neutral Lewis-acids are known in the art and are suitable forabstracting formal anionic ligands. See in particular the review articleby E. Y.-X. Chen and T. J. Marks, “Cocatalysts for Metal-CatalyzedOlefin Polymerization: Activators, Activation Processes, andStructure-Activity Relationships”, Chem. Rev., 100, 1391-1434 (2000).

When the cations of noncoordinating anion precursors are Bronsted acidssuch as protons or protonated Lewis bases (excluding water), orreducible Lewis acids such as ferrocenium or silver cations, or alkalior alkaline earth metal cations such as those of sodium, magnesium orlithium, the catalyst-precursor-to-activator molar ratio may be anyratio. Combinations of the described activator compounds may also beused for activation.

When an ionic or neutral stoichiometric activator is used, thecatalyst-precursor-to-activator molar ratio is from 1:10 to 1:1; 1:10 to10:1; 1:10 to 2:1; 1:10 to 3:1; 1:10 to 5:1; 1:2 to 1.2:1; 1:2 to 10:1;1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to 1.2:1; 1:3 to 10:1; 1:3 to2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1:1; 1:5 to 10:1; 1:5 to 2:1; 1:5 to3:1; 1:5 to 5:1; 1:1 to 1:1.2. The catalyst-precursor-to-co-activatormolar ratio is from 1:100 to 100:1; 1:75 to 75:1; 1:50 to 50:1; 1:25 to25:1; 1:15 to 15:1; 1:10 to 10:1; 1:5 to 5:1, 1:2 to 2:1; 1:100 to 1:1;1:75 to 1:1; 1:50 to 1:1; 1:25 to 1:1; 1:15 to 1:1; 1:10 to 1:1; 1:5 to1:1; 1:2 to 1:1; 1:10 to 2:1.

Preferred activators and activator/co-activator combinations includemethylalumoxane, modified methylalumoxane, mixtures of methylalumoxanewith dimethylanilinium tetrakis(pentafluorophenyl)borate ortris(pentafluorophenyl)boron, and mixtures of trimethyl aluminum withdimethylanilinium tetrakis(pentafluorophenyl)borate ortris(pentafluorophenyl)boron.

In some embodiments, scavenging compounds are used with stoichiometricactivators. Typical aluminum or boron alkyl components useful asscavengers are represented by the general formula R^(x)JZ₂ where J isaluminum or boron, R^(x) is as previously defined above, and each Z isindependently R^(x) or a different univalent anionic ligand such ashalogen (Cl, Br, I), alkoxide (OR^(x)) and the like. Most preferredaluminum alkyls include triethylaluminum, diethylaluminum chloride,tri-iso-butylaluminum, tri-n-octylaluminum, tri-n-hexylaluminum,trimethylaluminum and the like. Preferred boron alkyls includetriethylboron. Scavenging compounds may also be alumoxanes and modifiedalumoxanes including methylalumoxane and modified methylalumoxane.

Mixed Catalysts

The metallocene compounds of the invention can also be used in mixedcatalyst systems where, for example, the invention catalyst is used inconjunction with a “second catalyst” in the same reactor or in a seriesof reactors and where the invention catalyst produces oligomers,macromers, or polymers with olefinic end-groups, and the “secondcatalyst” incorporates these oligomers, macromers, or polymers into apolymer backbone as a copolymer with other monomers, such as ethylene,propylene, butene, and other C2 to C20 olefins. Alternatively, theinvention catalyst can be used in conjunction with a second catalyst inthe same reactor or in a series of reactors where the second catalystproduces oligomers, macromers, or polymers with olefinic end-groups, andthe invention catalyst incorporates these oligomers, macromers, orpolymers into a polymer backbone as a copolymer with other monomers,such as ethylene, propylene, butene, and other C2 to C20 olefins. The“second catalyst” can be of the same family as the invention catalyst,or can be from a completely different catalyst family. Likewise, theinvention catalyst can be used in conjunction with a “second catalyst”in the same reactor or in a series of reactors where the inventioncatalyst and the “second catalyst” produces mixtures or blends ofpolymers.

Suitable additional olefin polymerization catalysts for use as the“second catalyst” in a mixed catalyst system include any of thecompositions well known in the art to catalyze the olefin to polyolefinreaction. For example, the “second catalyst” can include any Group 4-6metallocene compound, such as the bridged and unbridged compoundscontaining one or two cyclopentadienyl-containing ligands. Typicalcatalysts and their precursors are well known in the art. Suitabledescription appears in the patent literature, for example U. S. Pat.Nos. 4,871,705, 4,937,299, and 5,324,800, EP-A-0418044, EP-A-0591756,WO-A-92/00333 and WO-A-94/01471.

Mixed catalyst systems can also use non-cyclopentadienyl, Group 4 or 5precursor compounds as the additional olefin polymerization catalyst.Non-cyclopentadienyl, Group 4 or 5 precursor compounds are activable tostable, discrete cationic complexes include those containing bulky,chelating, diamide ligands, such as described in U.S. Pat. No. 5,318,935and “Conformationally Rigid Diamide Complexes: Synthesis and Structureof Tantalum (III) Alkyne Derivatives”, D. H. McConville, et al,Organometallics 1995, 14, 3154-3156. U.S. Pat. No. 5,318,935 describesbridged and unbridged, bis-amido catalyst compounds of Group 4 metalscapable of α-olefins polymerization. Bridged bis(arylamido) Group 4compounds for olefin polymerization are described by D. H. McConville,et al., in Organometallics 1995, 14, 5478-5480. In addition, D. H.McConville, et al, Macromolecules 1996, 29, 5241-5243, describe bridgedbis(arylamido) Group 4 compounds that are polymerization catalysts for1-hexene. Cationic Group-3- or Lanthanide olefin polymerizationcomplexes are disclosed in U.S. Pat. No. 6,403,773.

Mixed catalyst systems can also use transition metal catalyst precursorsthat have a 2+ oxidation state as the additional olefin polymerizationcatalyst. Typical Ni²⁺ and Pd²⁺ complexes are diimines, see “New Pd(II)-and Ni(II)-Based Catalysts for Polymerization of Ethylene andα-Olefins”, M. Brookhart, et al, J. Am. Chem. Soc., 1995, 117,6414-6415, WO 96/23010 and WO 97/02298. See additionally the relatedbis(imino) Group 8 and 9 organometallic compounds described by V. C.Gibson and others in “Novel olefin polymerization catalysts based oniron and cobalt”, Chem. Commun., 849-850, 1998.

For a review of other potential catalysts used in combination or serieswith the invention catalysts, see S. D. Ittel and L. K. Johnson, Chem.Rev. 2000, 1000, 1169 and V. C. Gibson and S. K. Spitzmesser, Chem. Rev.2003, 103, 283.

Supported Catalysts

The catalyst compounds of this invention may be placed on a support. Toprepare uniform supported catalysts, the catalyst precursor ispreferably dissolved in a suitable solvent and then the resultantsolution is applied to or mixed with the support. The term “uniformsupported catalyst” means that the catalyst precursor, the activator andor the activated catalyst approach uniform distribution upon thesupport's accessible surface area, including the interior pore surfacesof porous supports. Some embodiments of supported catalysts preferuniform supported catalysts; other embodiments show no such preference.

Supported catalyst systems may be prepared by any method effective tosupport other coordination catalyst systems, effective meaning that thecatalyst so prepared can be used for oligomerizing or polymerizingolefin in a heterogenous process. The catalyst precursor, activator,co-activator if needed, suitable solvent, and support may be added inany order or simultaneously.

By one method, the activator, dissolved in an appropriate solvent suchas toluene may be stirred with the support material for 1 minute to 10hours. The total solution volume may be greater than the pore volume ofthe support, but some embodiments limit the total solution volume belowthat needed to form a gel or slurry (about 90% to 400%, preferably about100-200% of the pore volume). The mixture is optionally heated from30-200° C. during this time. The catalyst precursor may be added to thismixture as a solid, if a suitable solvent is employed in the previousstep, or as a solution. Or alternatively, this mixture can be filtered,and the resulting solid mixed with a catalyst precursor solution.Similarly, the mixture may be vacuum dried and mixed with a catalystprecursor solution. The resulting catalyst mixture is then stirred for 1minute to 10 hours, and the catalyst is either filtered from thesolution and vacuum dried or evaporation alone removes the solvent.

Alternatively, the catalyst precursor and activator may be combined insolvent to form a solution. Then the support is added, and the mixtureis stirred for 1 minute to 10 hours. The total solution volume may begreater than the pore volume of the support, but some embodiments limitthe total solution volume below that needed to form a gel or slurry(about 90% to 400%, preferably about 100-200% of the pore volume). Afterstirring, the residual solvent is removed under vacuum, typically atambient temperature and over 10-16 hours. But greater or lesser timesand temperatures are possible.

The catalyst precursor may also be supported absent the activator; inthat case, the activator (and co-activator if needed) is added to aslurry process's liquid phase. For example, a solution of catalystprecursor may be mixed with a support material for a period of about 1minute to 10 hours. The resulting precatalyst mixture may be filteredfrom the solution and dried under vacuum, or evaporation alone removesthe solvent. The total, catalyst-precursor-solution volume may begreater than the support's pore volume, but some embodiments limit thetotal solution volume below that needed to form a gel or slurry (about90% to 400%, preferably about 100-200% of the pore volume).

Additionally, two or more different catalyst precursors may be placed onthe same support using any of the support methods disclosed above.Likewise, two or more activators or an activator and co-activator may beplaced on the same support.

Suitable solid particle supports are typically comprised of polymeric orrefractory oxide materials, each being preferably porous. Any supportmaterial that has an average particle size greater than 10 μm issuitable for use in this invention. Various embodiments select a poroussupport material, such as for example, talc, inorganic oxides, inorganicchlorides, for example magnesium chloride and resinous support materialssuch as polystyrene, polyolefin or polymeric compounds or any otherorganic support material and the like. Some embodiments select inorganicoxide materials as the support material including Group-2, -3, -4, -5,-13, or -14 metal or metalloid oxides. Some embodiments select thecatalyst support materials to include silica, alumina, silica-alumina,and their mixtures. Other inorganic oxides may serve either alone or incombination with the silica, alumina, or silica-alumina. These aremagnesia, titania, zirconia, and the like. Lewis acidic materials suchas montmorillonite and similar clays may also serve as a support. Inthis case, the support can optionally double as the activator component.But additional activator may also be used.

The support material may be pretreated by any number of methods. Forexample, inorganic oxides may be calcined, chemically treated withdehydroxylating agents such as aluminum alkyls and the like, or both.

As stated above, polymeric carriers will also be suitable in accordancewith the invention, see for example the descriptions in WO 95/15815 andU.S. Pat. No. 5,427,991. The methods disclosed may be used with thecatalyst complexes, activators or catalyst systems of this invention toadsorb or absorb them on the polymeric supports, particularly if made upof porous particles, or may be chemically bound through functionalgroups bound to or in the polymer chains.

The catalyst supports used herein suitably have a surface area of from10-700 m²/g, a pore volume of 0.1-4.0 cc/g and an average particle sizeof 10-500 μm. Some embodiments select a surface area of 50-500 m²/g, apore volume of 0.5-3.5 cc/g, or an average particle size of 20-200 μm.Other embodiments select a surface area of 100-400 m²/g, a pore volumeof 0.8-3.0 cc/g, and an average particle size of 30-100 μm. Catalystsupports typically have a pore size of 10-1000 Angstroms, alternatively50-500 Angstroms, or 75-350 Angstroms.

The catalyst precursors of the invention are generally deposited on asupport at a loading level of 10-100 micromoles of catalyst precursorper gram of solid support; alternately 20-80 micromoles of catalystprecursor per gram of solid support; or 40-60 micromoles of catalystprecursor per gram of support. But greater or lesser values may be usedprovided that the total amount of solid catalyst precursor does notexceed the support's pore volume.

Monomers

When activated with a conventional activator, the halogenatedmetallocene compounds of the invention can be used to polymerize oroligomerize any unsaturated monomer or monomers. Preferred monomersinclude C₂ to C₁₀₀ olefins, preferably C₂ to C₆₀ olefins, preferably C₂to C₄₀ olefins preferably C₂ to C₂₀ olefins, preferably C₂ to C₁₂olefins. In some embodiments preferred monomers include linear, branchedor cyclic alpha-olefins, preferably C₂ to C₁₀₀ alpha-olefins, preferablyC₂ to C₆₀ alpha-olefins, preferably C₂ to C₄₀ alpha-olefins preferablyC₂ to C₂₀ alpha-olefins, preferably C₂ to C₁₂ alpha-olefins. Preferredolefin monomers may be one or more of ethylene, propylene, butene,pentene, hexene, heptene, octene, nonene, decene, dodecene,4-methylpentene-1, 3-methylpentene-1, 3,5,5-trimethylhexene-1, and5-ethylnonene-1.

In another embodiment the polymer produced herein is a copolymer of oneor more linear or branched C₃ to C₃₀ prochiral alpha-olefins or C₅ toC₃₀ ring containing olefins or combinations thereof capable of beingpolymerized by either stereospecific and non-stereospecific catalysts.Prochiral, as used herein, refers to monomers that favor the formationof isotactic or syndiotactic polymer when polymerized usingstereospecific catalyst(s).

Preferred monomers may also include aromatic-group-containing monomerscontaining up to 30 carbon atoms. Suitable aromatic-group-containingmonomers comprise at least one aromatic structure, preferably from oneto three, more preferably a phenyl, indenyl, fluorenyl, or naphthylmoiety. The aromatic-group-containing monomer further comprises at leastone polymerizable double bond such that after polymerization, thearomatic structure will be pendant from the polymer backbone. Thearomatic-group containing monomer may further be substituted with one ormore hydrocarbyl groups including but not limited to C₁ to C₁₀ alkylgroups. Additionally two adjacent substitutions may be joined to form aring structure. Preferred aromatic-group-containing monomers contain atleast one aromatic structure appended to a polymerizable olefinicmoiety. Particularly preferred aromatic monomers include styrene,alpha-methylstyrene, para-alkylstyrenes, vinyltoluenes,vinylnaphthalene, allyl benzene, and indene, especially styrene,para-methylstyrene, 4-phenyl-1-butene and allyl benzene.

Non aromatic cyclic group containing monomers can also be polymerized oroligomerized with the catalyst systems of the invention. These monomerscan contain up to 30 carbon atoms. Suitable non-aromatic cyclic groupcontaining monomers preferably have at least one polymerizable olefinicgroup that is either pendant on the cyclic structure or is part of thecyclic structure. The cyclic structure may also be further substitutedby one or more hydrocarbyl groups such as, but not limited to, C₁ to C₁₀alkyl groups. Preferred non-aromatic cyclic group containing monomersinclude vinylcyclohexane, vinylcyclohexene, cyclopentadiene,cyclopentene, 4-methylcyclopentene, cyclohexene, 4-methylcyclohexene,cyclobutene, vinyladamantane, norbornene, 5-methylnorbornene,5-ethylnorbornene, 5-propylnorbornene, 5-butylylnorbornene,5-pentylnorbornene, 5-hexylnorbornene, 5-heptylnorbornene,5-octylnorbornene, 5-nonylnorbornene, 5-decylnorbornene,5-phenylnorbornene, vinylnorbornene, ethylidene norbornene,5,6-dimethylnorbornene, 5,6-dibutylnorbornene and the like.

Preferred diolefin monomers useful in this invention include anyhydrocarbon structure, preferably C₄ to C₃₀, having at least twounsaturated bonds, wherein at least one, typically two, of theunsaturated bonds are readily incorporated into a polymer by either astereospecific or a non-stereospecific catalyst(s). It is furtherpreferred that the diolefin monomers be selected from alpha-omega-dienemonomers (i.e. di-vinyl monomers). More preferably, the diolefinmonomers are linear di-vinyl monomers, most preferably those containingfrom 4 to 30 carbon atoms. Examples of preferred dienes includebutadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene,decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene,pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene,nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene,tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene,octacosadiene, nonacosadiene, triacontadiene, particularly preferreddienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene,1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions.

Non-limiting examples of preferred polar unsaturated monomers useful inthis invention include nitro substituted monomers including6-nitro-1-hexene; amine substituted monomers includingN-methylallylamine, N-allylcyclopentylamine, and N-allyl-hexylamine;ketone substituted monomers including methyl vinyl ketone, ethyl vinylketone, and 5-hexen-2-one; aldehyde substituted monomers includingacrolein, 2,2-dimethyl-4-pentenal, undecylenic aldehyde, and2,4-dimethyl-2,6-heptadienal; alcohol substituted monomers includingallyl alcohol, 7-octen-1-ol, 7-octene-1,2-diol, 10-undecen-1-ol,10-undecene-1,2-diol, 2-methyl-3-buten-1-ol; acetal, epoxide and orether substituted monomers including4-hex-5-enyl-2,2-dimethyl-[1,3]dioxolane, 2,2-dimethyl-4-non-8-enyl-[1,3]dioxolane, acrolein dimethyl acetal,butadiene monoxide, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene,1,2-epoxy-5-hexene, 2-methyl-2-vinyloxirane, allyl glycidyl ether,2,5-dihydrofuran, 2-cyclopenten-1-one ethylene ketal, 11-methoxyundec-1-ene, and 8-methoxyoct-1-ene; sulfur containing monomersincluding allyl disulfide; acid and ester substituted monomers includingacrylic acid, vinylacetic acid, 4-pentenoic acid,2,2-dimethyl-4-pentenoic acid, 6-heptenoic acid, trans-2,4-pentadienoicacid, 2,6-heptadienoic acid, methyl acrylate, ethyl acrylate, tert-butylacrylate, n-butyl acrylate, methacrylic acid, methyl methacrylate, ethylmethacrylate, tert-butyl methacrylate, n-butyl methacrylate,hydroxypropyl acrylate, acetic acid oct-7-enyl ester, non-8-enoic acidmethyl ester, acetic acid undec-10-enyl ester, dodec-11-enoic acidmethyl ester, propionic acid undec-10-enyl ester, dodec-11-enoic acidethyl ester, and nonylphenoxypolyetheroxy acrylate; siloxy containingmonomers including trimethyloct-7-enyloxy silane, andtrimethylundec-10-enyloxy silane, polar functionalized norbornenemonomers including 5-norbornene-2-carbonitrile,5-norbornene-2-carboxaldehyde, 5-norbornene-2-carboxylic acid,cis-5-norbornene-endo-2,3-dicarboxylic acid,5-norbornene-2,2,-dimethanol, cis-5-norbornene-endo-2,3-dicarboxylicanhydride, 5-norbornene-2-endo-3-endo-dimethanol,5-norbornene-2-endo-3-exo-dimethanol, 5-norbornene-2-methanol,5-norbornene-2-ol, 5-norbornene-2-yl acetate,1-[2-(5-norbornene-2-yl)ethyl]-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane,2-benzoyl-5-norbornene, 2-acetyl-5-norbornene, 7-synmethoxymethyl-5-norbornen-2-one, 5-norbornen-2-ol, and5-norbornen-2-yloxy-trimethylsilane, and partially fluorinated monomersincluding nonafluoro-1-hexene, allyl-1,1,2,2,-tetrafluoroethyl ether,2,2,3,3-tetrafluoro-non-8-enoic acid ethyl ester,1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoro-oct-7-enyloxy)-ethanesulfonylfluoride, acrylic acid2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluoro-octyl ester, and1,1,2,2-tetrafluoro-2-(1,1,2,2,3,3,4,4-octafluoro-dec-9-enyloxy)-ethanesulfonylfluoride.

In an embodiment herein, the process described herein is used to producean oligomer of any of the monomers listed above. Preferred oligomersinclude oligomers of any C₂ to C₂₀ olefins, preferably C₂ to C₁₂alpha-olefins, most preferably oligomers comprising ethylene, propyleneand or butene are prepared. A preferred feedstock for theoligomerization process is the alpha-olefin, ethylene. But otheralpha-olefins, including but not limited to propylene and 1-butene, mayalso be used alone or combined with ethylene. Preferred alpha-olefinsinclude any C₂ to C₄₀ alpha-olefin, preferably any C₂ to C₂₀alpha-olefin, preferably any C₂ to C₁₂ alpha-olefin, preferablyethylene, propylene, and butene, most preferably ethylene. Dienes may beused in the processes described herein, preferably alpha-omega-dienesare used alone or in combination with mono-alpha olefins.

In a preferred embodiment the process described herein may be used toproduce homopolymers or copolymers. (For the purposes of this inventionand the claims thereto a copolymer may comprise two, three, four or moredifferent monomer units.) Preferred polymers produced herein includehomopolymers or copolymers of any of the above monomers. In a preferredembodiment the polymer is a homopolymer of any C₂ to C₁₂ alpha-olefin.Preferably the polymer is a homopolymer of ethylene or a homopolymer ofpropylene. In another embodiment the polymer is a copolymer comprisingethylene and one or more of any of the monomers listed above. In anotherembodiment the polymer is a copolymer comprising propylene and one ormore of any of the monomers listed above. In another preferredembodiment the homopolymers or copolymers described, additionallycomprise one or more diolefin comonomers, preferably one or more C₄ toC₄₀ diolefins.

In another preferred embodiment the polymer produced herein is acopolymer of ethylene and one or more C₃ to C₂₀ linear, branched orcyclic monomers, preferably one or more C₃ to C₁₂ linear, branched orcyclic alpha-olefins. Preferably the polymer produced herein is acopolymer of ethylene and one or more of propylene, butene, pentene,hexene, heptene, octene, nonene, decene, dodecene, 4-methylpentene-1,3-methylpentene-1,3,5,5-trimethylhexene-1, cyclopentene,4-methylcyclopentene, cyclohexene, and 4-methylcyclohexene.

In another preferred embodiment the polymer produced herein is acopolymer of propylene and one or more C₂ or C₄ to C₂₀ linear, branchedor cyclic monomers, preferably one or more C₂ or C₄ to C₁₂ linear,branched or cyclic alpha-olefins. Preferably the polymer produced hereinis a copolymer of propylene and one or more of ethylene, butene,pentene, hexene, heptene, octene, nonene, decene, dodecene,4-methylpentene-1,3-methylpentene-1, and 3,5,5-trimethylhexene-1.

In a preferred embodiment, the polymer produced herein is a homopolymerof norbornene or a copolymer of norbornene and a substituted norbornene,including polar functionalized norbornenes.

In a preferred embodiment the copolymers described herein comprise atleast 50 mole % of a first monomer and up to 50 mole % of othermonomers.

In another embodiment, the polymer comprises:

-   -   (a) a first monomer present at from 40 to 95 mole %, preferably        50 to 90 mole %, preferably 60 to 80 mole %, and    -   (b) a comonomer present at from 5 to 60 mole %, preferably 10 to        40 mole %, more preferably 20 to 40 mole %, and    -   (c) a termonomer present at from 0 to 10 mole %, more preferably        from 0.5 to 5 mole %, more preferably 1 to 3 mole %.

In a preferred embodiment the first monomer (a) comprises one or more ofany C₃ to C₈ linear branched or cyclic alpha-olefins, includingpropylene, butene, (and all isomers thereof), pentene (and all isomersthereof), hexene (and all isomers thereof), heptene (and all isomersthereof), and octene (and all isomers thereof). Preferred monomersinclude propylene, 1-butene, 1-hexene, 1-octene, cyclopentene,cyclohexene, cyclooctene, hexadiene, cyclohexadiene and the like.

In a preferred embodiment the comonomer (b) comprises one or more of anyC₂ to C₄₀ linear, branched or cyclic alpha-olefins (provided ethylene,if present, is present at 5 mole % or less), including ethylene,propylene, butene, pentene, hexene, heptene, and octene, nonene, decene,undecene, dodecene, hexadecene, butadiene, hexadiene, heptadiene,pentadiene, octadiene, nonadiene, decadiene, dodecadiene, styrene,3,5,5-trimethylhexene-1, 3-methylpentene-1, 4-methylpentene-1,cyclopentadiene, and cyclohexene.

In a preferred embodiment the termonomer (c) comprises one or more ofany C₂ to C₄₀ linear, branched or cyclic alpha-olefins, (providedethylene, if present, is present at 5 mole % or less), includingethylene, propylene, butene, pentene, hexene, heptene, and octene,nonene, decene, undecene, dodecene, hexadecene, butadiene, hexadiene,heptadiene, pentadiene, octadiene, nonadiene, decadiene, dodecadiene,styrene, 3,5,5-trimethylhexene-1, 3-methylpentene-1, 4-methylpentene-1,cyclopentadiene, and cyclohexene.

In a preferred embodiment the monomers described above further compriseone or more dienes at up to 10 weight %, preferably at 0.00001 to 1.0weight %, preferably 0.002 to 0.5 weight %, even more preferably 0.003to 0.2 weight %, based upon the total weight of the composition. In someembodiments 500 ppm or less of diene is added to the polymerization,preferably 400 ppm or less, preferably or 300 ppm or less. In otherembodiments at least 50 ppm of diene is added to the polymerization, or100 ppm or more, or 150 ppm or more.

Polymerization Processes

Invention catalyst complexes are useful in polymerizing unsaturatedmonomers conventionally known to undergo metallocene-catalyzedpolymerization such as solution, slurry, gas-phase, and high-pressurepolymerization. Typically one or more transition metal compounds, one ormore activators, and one or more monomers are contacted to producepolymer. These catalysts may be supported and as such will beparticularly useful in the known, fixed-bed, moving-bed, fluid-bed,slurry, solution, or bulk operating modes conducted in single, series,or parallel reactors.

One or more reactors in series or in parallel may be used in the presentinvention. The transition metal compound, activator and when required,co-activator, may be delivered as a solution or slurry, eitherseparately to the reactor, activated in-line just prior to the reactor,or preactivated and pumped as an activated solution or slurry to thereactor. Polymerizations are carried out in either single reactoroperation, in which monomer, comonomers,catalyst/activator/co-activator, optional scavenger, and optionalmodifiers are added continuously to a single reactor or in seriesreactor operation, in which the above components are added to each oftwo or more reactors connected in series. The catalyst components can beadded to the first reactor in the series. The catalyst component mayalso be added to both reactors, with one component being added to firstreaction and another component to other reactors. In one preferredembodiment, the precatalyst is activated in the reactor in the presenceof olefin.

Ethylene-alpha-olefin (including ethylene-cyclic olefin andethylene-alpha -olefin-diolefin) elastomers of high molecular weight andlow crystallinity can be prepared utilizing the catalysts of theinvention under traditional solution processes or by introducingethylene gas into a slurry utilizing the alpha-olefin or cyclic olefinor mixture thereof with other monomers, polymerizable and not, as apolymerization diluent in which the catalyst suspension is suspended.Typical ethylene pressures will be between 10 and 1000 psig (69-6895kPa) and the polymerization diluent temperature will typically bebetween −10 and 160° C. The process can be carried out in a stirred tankreactor or a tubular reactor, or more than one reactor operated inseries or in parallel. See the disclosure of U.S. Pat. No. 5,001,205 forgeneral process conditions. All documents are incorporated by referencefor description of polymerization processes, ionic activators and usefulscavenging compounds.

The invention catalyst compositions can be used individually or can bemixed with other known polymerization catalysts to prepare polymerblends. Monomer and catalyst selection allows polymer blend preparationunder conditions analogous to those using individual catalysts. Polymershaving increased MWD for improved processing and other traditionalbenefits available from polymers made with mixed catalyst systems canthus be achieved.

Generally, when using invention catalysts, particularly when they areimmobilized on a support, the complete catalyst system will additionallycomprise one or more scavenging compounds. Here, the term scavengingcompound means a compound that removes polar impurities from thereaction environment. These impurities adversely affect catalystactivity and stability. Typically, purifying steps are usually usedbefore introducing reaction components to a reaction vessel. But suchsteps will rarely allow polymerization without using some scavengingcompounds. Normally, the polymerization process will still use at leastsmall amounts of scavenging compounds.

Typically, the scavenging compound will be an organometallic compoundsuch as the Group-13 organometallic compounds of U.S. Pat. Nos.5,153,157, 5,241,025 and WO-A-91/09882, WO-A-94/03506, WO-A-93/14132,and that of WO 95/07941. Exemplary compounds include triethyl aluminum,triethyl borane, tri-iso-butyl aluminum, methyl alumoxane, iso-butylalumoxane, and tri-n-octyl aluminum. Those scavenging compounds havingbulky or C₆-C₂₀ linear hydrocarbyl substituents connected to the metalor metalloid center usually minimize adverse interaction with the activecatalyst. Examples include triethylaluminum, but more preferably, bulkycompounds such as tri-iso-butyl aluminum, tri-iso-phenyl aluminum, andlong-chain linear alkyl-substituted aluminum compounds, such astri-n-hexyl aluminum, tri-n-octyl aluminum, or tri-n-dodecyl aluminum.When alumoxane is used as the activator, any excess over that needed foractivation will scavenge impurities and additional scavenging compoundsmay be unnecessary. Alumoxanes also may be added in scavengingquantities with other activators, e.g., methylalumoxane,[Me₂HNPh]⁺[B(pfP)₄]⁻ or B(pfp)₃ (perfluorophenyl=pfP=C₆F₅).

In terms of polymer density, the polymers capable of production inaccordance the invention, can range from about 0.85 to about 0.95,preferably from 0.87 to 0.93, more preferably 0.89 to 0.920. Polymermolecular weights can range from about 3000 Mn to about 2,000,000 Mn orgreater. Molecular weight distributions can range from about 1.1 toabout 50.0, with molecular weight distributions from 1.2 to about 5.0being more typical. Pigments, antioxidants and other additives, as isknown in the art, may be added to the polymer.

Gas Phase Polymerization

Generally, in a fluidized gas bed process used for producing polymers, agaseous stream containing one or more monomers is continuously cycledthrough a fluidized bed in the presence of a catalyst under reactiveconditions. The gaseous stream is withdrawn from the fluidized bed andrecycled back into the reactor. Simultaneously, polymer product iswithdrawn from the reactor and fresh monomer is added to replace thepolymerized monomer. (See for example U.S. Pat. Nos. 4,543,399,4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304,5,453,471, 5,462,999, 5,616,661 and 5,668,228 all of which are fullyincorporated herein by reference.).

The reactor pressure in a gas phase process may vary from about 10 psig(69 kPa) to about 500 psig (3448 kPa), preferably from about 100 psig(690 kPa) to about 500 psig (3448 kPa), preferably in the range of fromabout 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferablyin the range of from about 250 psig (1724 kPa) to about 350 psig (2414kPa).

The reactor temperature in the gas phase process may vary from about 30°C. to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 70° C. to 110° C., and mostpreferably in the range of from about 70° C. to about 95° C. In anotherembodiment when high density polyethylene is desired then the reactortemperature is typically between 70 and 105° C.

The productivity of the catalyst or catalyst system in a gas phasesystem is influenced by the partial pressure of the main monomer. Thepreferred mole percent of the main monomer, ethylene or propylene,preferably ethylene, is from about 25 to 90 mole percent and thecomonomer partial pressure is in the range of from about 138 kPa toabout 517 kPa, preferably about 517 kPa to about 2069 kPa, which aretypical conditions in a gas phase polymerization process. Also in somesystems the presence of comonomer can increase productivity.

In a preferred embodiment, the reactor utilized in the present inventionis capable of producing more than 500 lbs of polymer per hour (227Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher, preferablygreater than 1000 lbs/hr (455 Kg/hr), more preferably greater than10,000 lbs/hr (4540 Kg/hr), even more preferably greater than 25,000lbs/hr (11,300 Kg/hr), still more preferably greater than 35,000 lbs/hr(15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr(22,700 Kg/hr) and preferably greater than 65,000 lbs/hr (29,000 Kg/hr)to greater than 100,000 lbs/hr (45,500 Kg/hr), and most preferably over100,000 lbs/hr (45,500 Kg/hr).

Other gas phase processes contemplated by the process of the inventioninclude those described in U.S. Pat. Nos. 5,627,242, 5,665,818 and5,677,375, and European publications EP-A-0794 200, EP-A-0 802 202 andEP-B-634 421 all of which are herein fully incorporated by reference.

In another preferred embodiment the catalyst system in is liquid formand is introduced into the gas phase reactor into a resin particle leanzone. For information on how to introduce a liquid catalyst system intoa fluidized bed polymerization into a particle lean zone, please seeU.S. Pat. No. 5,693,727, which is incorporated by reference herein.

Slurry Phase Polymerization

A slurry polymerization process generally operates between 1 to about 50atmosphere pressure range (15 psig to 735 psig, 103 kPa to 5068 kPa) oreven greater and temperatures in the range of 0° C. to about 120° C. Ina slurry polymerization, a suspension of solid, particulate polymer isformed in a liquid polymerization diluent medium to which monomer andcomonomers along with catalyst are added. The suspension includingdiluent is intermittently or continuously removed from the reactor wherethe volatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process should be operatedabove the reaction diluent critical temperature and pressure.Preferably, a hexane or an isobutane medium is employed.

In one embodiment, a preferred polymerization technique of the inventionis referred to as a particle form polymerization, or a slurry processwhere the temperature is kept below the temperature at which the polymergoes into solution. Such technique is well known in the art, anddescribed in for instance U.S. Pat. No. 3,248,179 which is fullyincorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 85° C. to about 110°C. Two preferred polymerization methods for the slurry process are thoseemploying a loop reactor and those utilizing a plurality of stirredreactors in series, parallel, or combinations thereof. Non-limitingexamples of slurry processes include continuous loop or stirred tankprocesses. Also, other examples of slurry processes are described inU.S. Pat. No. 4,613,484, which is herein fully incorporated byreference.

In another embodiment, the slurry process is carried out continuously ina loop reactor. The catalyst, as a slurry in isobutane or as a dry freeflowing powder, is injected regularly to the reactor loop, which isitself filled with circulating slurry of growing polymer particles in adiluent of isobutane containing monomer and comonomer. Hydrogen,optionally, may be added as a molecular weight control. The reactor ismaintained at a pressure of 3620 kPa to 4309 kPa and at a temperature inthe range of about 60° C. to about 104° C. depending on the desiredpolymer melting characteristics. Reaction heat is removed through theloop wall since much of the reactor is in the form of a double-jacketedpipe. The slurry is allowed to exit the reactor at regular intervals orcontinuously to a heated low pressure flash vessel, rotary dryer and anitrogen purge column in sequence for removal of the isobutane diluentand all unreacted monomer and comonomers. The resulting hydrocarbon freepowder is then compounded for use in various applications.

In another embodiment, the reactor used in the slurry process of theinvention is capable of and the process of the invention is producinggreater than 2000 lbs of polymer per hour (907 Kg/hr), more preferablygreater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactorused in the process of the invention is producing greater than 15,000lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

In another embodiment in the slurry process of the invention the totalreactor pressure is in the range of from 400 psig (2758 kPa) to 800 psig(5516 kPa), preferably 450 psig (3103 kPa) to about 700 psig (4827 kPa),more preferably 500 psig (3448 kPa) to about 650 psig (4482 kPa), mostpreferably from about 525 psig (3620 kPa) to 625 psig (4309 kPa).

In yet another embodiment in the slurry process of the invention theconcentration of predominant monomer in the reactor liquid medium is inthe range of from about 1 to 10 weight percent, preferably from about 2to about 7 weight percent, more preferably from about 2.5 to about 6weight percent, most preferably from about 3 to about 6 weight percent.

Another process of the invention is where the process, preferably aslurry or gas phase process is operated in the absence of or essentiallyfree of any scavengers, such as triethylaluminum, trimethylaluminum,tri-iso-butylaluminum and tri-n-hexylaluminum and diethyl aluminumchloride, dibutyl zinc and the like. This process is described in PCTpublication WO 96/08520 and U.S. Pat. No. 5,712,352, which are hereinfully incorporated by reference.

In another embodiment the process is run with scavengers. Typicalscavengers include trimethyl aluminum, tri-iso-butyl aluminum and anexcess of alumoxane or modified alumoxane.

In a preferred embodiment, hydrogen or other chain termination agent(such as phenylsilane) are added to the slurry polymerization.Homogeneous, bulk or solution phase polymerization

The catalysts described herein can be used advantageously in homogeneoussolution processes. Generally this involves polymerization in acontinuous reactor in which the polymer formed and the starting monomerand catalyst materials supplied, are agitated to reduce or avoidconcentration gradients. Suitable processes operate above the meltingpoint of the polymers at high pressures, from 1 to 3000 bar (10-30,000MPa), in which the monomer acts as diluent or in solution polymerizationusing a solvent.

Temperature control in the reactor is obtained by balancing the heat ofpolymerization and with reactor cooling by reactor jackets or coolingcoils to cool the contents of the reactor, auto refrigeration,pre-chilled feeds, vaporization of liquid medium (diluent, monomers orsolvent) or combinations of all three. Adiabatic reactors withpre-chilled feeds may also be used. The reactor temperature depends onthe catalyst used. In general, the reactor temperature preferably canvary between about 0° C. and about 160° C., more preferably from about10° C. to about 140° C., and most preferably from about 40° C. to about120° C. In series operation, the second reactor temperature ispreferably higher than the first reactor temperature. In parallelreactor operation, the temperatures of the two reactors are independent.The pressure can vary from about 1 mm Hg to 2500 bar (25,000 MPa),preferably from 0.1 bar to 1600 bar (1-16,000 MPa), most preferably from1.0 to 500 bar (10-5000 MPa).

Each of these processes may also be employed in single reactor, parallelor series reactor configurations. The liquid processes comprisecontacting olefin monomers with the above described catalyst system in asuitable diluent or solvent and allowing said monomers to react for asufficient time to produce the desired polymers. Hydrocarbon solventsare suitable, both aliphatic and aromatic. Alkanes, such as hexane,pentane, isopentane, and octane, are preferred.

The process can be carried out in a continuous stirred tank reactor,batch reactor, or plug flow reactor, or more than one reactor operatedin series or parallel. These reactors may have or may not have internalcooling and the monomer feed may or may not be refrigerated. See thegeneral disclosure of U.S. Pat. No. 5,001,205 for general processconditions. See also, international application WO 96/33227 and WO97/22639.

Medium and High Pressure Polymerizations

In the high pressure process for the polymerization of ethylene alone orin combination with C₃ to C₁₀ alpha-olefins and optionally othercopolymerizable olefins, the temperature of the medium within which thepolymerization reaction occurs is at least 120° C. and preferably above140° C. and may range to 350° C., but below the decompositiontemperature of said polymer product, typically from 310° C. to 325° C.Preferably, the polymerization is completed at a temperature within therange of 130° C. to 230° C. The polymerization is completed at apressure above 200 bar (20 MPa), and generally at a pressure within therange of 500 bar (50 MPa) to 3500 bar (350 MPa). Preferably, thepolymerization is completed at a pressure within the range from 800 bar(80 MPa) to 2500 bar (250 MPa).

For a medium pressure process, the temperature within which thepolymerization reaction occurs is at least 80° C. and typically rangesfrom 80° C. to 250° C., preferably from 100° C. to 220° C., and shouldfor a given polymer in the reactor, be above the melting point of saidpolymer so as to maintain the fluidity of the polymer-rich phase. Thepressure can be varied between 100 and 1000 bar for ethylenehomopolymers and from 30 bar (3 MPa) to 1000 bar (100 MPa), especially50 bar (5 MPa) to 500 bar (50 MPa) for processes producing ethylenecopolymers containing C₃ to C₁₀ olefins and optionally othercopolymerizable olefins.

After polymerization and deactivation of the catalyst, the polymerproduct can be recovered by processes well known in the art. Any excessreactants may be flashed off from the polymer and the polymer obtainedextruded into water and cut into pellets or other suitable comminutedshapes. For general process conditions, see the general disclosure ofU.S. Pat. Nos. 5,084,534, 5,408,017, 6,127,497, 6,255,410, which areincorporated herein by reference.

In another embodiment, this invention relates to:

-   1. A metallocene compound comprising a transition metal and at least    one substituted monocyclic or polycyclic arene ligand bonded to the    transition metal, wherein said arene ligand comprises at least one    halogen substituent directly bonded to an sp² carbon atom at a    bondable ring position of an aromatic five-membered ring of said    arene ligand.-   2. The metallocene compound of paragraph 1 and including a first    substituted indenyl ligand pi-bonded to the transition metal,    wherein said first ligand comprises at least one halogen substituent    directly bonded to an sp² carbon atom at the one, two or three    position of the indenyl ligand.-   3. The metallocene compound of paragraph 1 and including a first    substituted fluorenyl ligand pi-bonded to the transition metal,    wherein said first ligand comprises at least one halogen substituent    directly bonded to an sp² carbon atom at the nine position of the    fluorenyl ligand.-   4. The metallocene compound of any one of paragraphs 1 to 3 and    including a second monoanionic ligand bonded to the transition    metal.-   5. The metallocene compound of paragraph 4 wherein said second    monoanionic ligand is a substituted or unsubstituted monocyclic or    polycyclic ligand pi-bonded to the transition metal.-   6. The metallocene compound of paragraph 4 wherein said second    monoanionic ligand is a substituted or unsubstituted monocyclic or    polycyclic arene ligand pi-bonded to the transition metal.-   7. The metallocene compound of paragraph 4 wherein said second    monoanionic ligand is a substituted or unsubstituted indenyl ligand    or a substituted or unsubstituted fluorenyl ligand.-   8. The metallocene compound of any preceding paragraph 1 to 7    wherein the transition metal is from a Group 3, 4, 5 or 6 of the    Periodic Table of Elements, or a lanthanide metal or an actinide    metal.-   9. A metallocene compound represented by the formula (1):    wherein-   M is a Group 3, 4, 5 or 6 transition metal atom, or a lanthanide    metal atom, or actinide metal atom, and preferably is a Group 4    transition metal selected from titanium, zirconium and hafnium;-   E is a substituted polycyclic arene ligand pi-bonded to M and    including at least one halogen substituent directed bonded to an sp²    carbon atom at a bondable ring position of an aromatic five-membered    ring of said arene ligand;-   A is a monanionic ligand bonded to M;-   Y is bonded to A and to any single bondable position of the ring    structure of E, and is a bridging group containing a Group 13, 14,    15, or 16 element, and is present when y is one and absent when y is    zero;-   y is zero or one; and-   each X is a univalent anionic ligand, or two X are joined and bound    to the metal atom to form a metallocycle ring, or two X are joined    to form a chelating ligand, a diene ligand, or an alkylidene ligand.-   10. The metallocene compound of paragraph 9 wherein E is a    substituted indenyl ligand and said at least one halogen substituent    is connected to the one, two or three position of the indenyl    ligand.-   11. The metallocene compound of paragraph 9 wherein E is a    substituted fluorenyl ligand and said at least one halogen    substituent is connected to the nine position of the fluorenyl    ligand.-   12. The metallocene compound of any one of paragraphs 9 to 11    wherein A is a substituted or unsubstituted monocyclic or polycyclic    ligand, preferably a substituted or unsubstituted monocyclic or    polycyclic arene ligand, more preferably a substituted or    unsubstituted indenyl ligand or fluorenyl ligand, pi-bonded to M.-   13. A metallocene compound represented by the formula (2):    wherein-   M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanide    metal atom, or actinide metal atom, and preferably is a Group 4    transition metal selected from titanium, zirconium and hafnium;-   R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ are, independently, hydrogen, or a    hydrocarbyl, substituted hydrocarbyl, halogen, halocarbyl,    substituted halocarbyl, silylcarbyl, substituted silylcarbyl,    germylcarbyl, substituted germylcarbyl, or other heteroatom    substituents wherein the heteroatom is bonded directly to a ring    carbon atom of the indenyl ligand and is boron, a Group 14 atom that    is not carbon, a Group 15 atom, or a Group 16 atom, and adjacent R¹,    R², R³, R⁴, R⁵, R⁶, and R⁷ may be joined together to form a    substituted or unsubstituted, saturated, partially unsaturated, or    aromatic cyclic or polycyclic substituent;-   Y is an optional bridging group that contains a Group 13, 14, 15, or    16 element, and that is bonded to A and to any single bondable    position of the indenyl ligand, and is present when y is one and    absent when y is zero, and when present, Y replaces one of R¹, R²,    R³, R⁴, R⁵, R⁶, and R⁷ in formula (2);-   y is zero or one;-   A is a substituted or unsubstituted cyclopentadienyl ligand, a    substituted or unsubstituted indenyl ligand, or a substituted or    unsubstituted fluorenyl ligand; and-   each X is a univalent anionic ligand, or two X are joined and bound    to the metal atom to form a metallocycle ring, or two X are joined    to form a chelating ligand, a diene ligand, or an alkylidene ligand;-   provided that at least one of R¹, R₂ and R₃ is a halogen    substituent,-   14. A metallocene compound represented by the formula (3):    wherein-   M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanide    metal atom, or actinide metal atom, and preferably is a Group 4    transition metal selected from titanium, zirconium and hafnium;-   R^(1′), R^(2′), R^(3′), R^(4′), R^(5′), R^(6′), R^(7 ′) and R^(8′)    are, independently, hydrogen, or a hydrocarbyl, substituted    hydrocarbyl, halogen, halocarbyl, substituted halocarbyl,    silylcarbyl, substituted silylcarbyl, germylcarbyl, substituted    germylcarbyl, or other heteroatom substituents wherein the    heteroatom is bonded directly to a ring carbon atom of the fluorenyl    ligand and is boron, a Group 14 atom that is not carbon, a Group 15    atom, or a Group 16 atom, and adjacent R^(1′), R^(2′), R^(3′),    R^(4′), R^(5′), R^(6′), R^(7′) and R^(8′) may be joined together to    form a substituted or unsubstituted, saturated, partially    unsaturated, or aromatic cyclic or polycyclic substituent;-   R⁹′ is a halogen substituent;-   Y is an optional bridging group that contains a Group 13, 14, 15, or    16 element, and that is bonded to A and to any single bondable    position of the fluorenyl ligand, and is present when y is one and    absent when y is zero, and when present, Y replaces one of R^(1′),    R^(2′), R^(3′), R^(4′), R^(5′), R^(6′), R^(7′) and R^(8′) in formula    (3);-   y is zero or one;-   A is a substituted or unsubstituted cyclopentadienyl ligand, a    substituted or unsubstituted indenyl ligand, or a substituted or    unsubstituted fluorenyl ligand; and-   each X is a univalent anionic ligand, or two X are joined and bound    to the metal atom to form a metallocycle ring, or two X are joined    to form a chelating ligand, a diene ligand, or an alkylidene ligand.-   15. The compound of any one of paragraphs 9 to 14 wherein Y is    present and is a bridging group containing boron or a Group 14, 15    or 16 element.-   16. The compound of any one of paragraphs 9 to 15 wherein Y is    present and is selected from S, O, NR′, PR′, AsR′, SbR′, O—O, S—S,    R′N—NR′, R′P—PR′, O—S, O—NR′, O—PR′, S—NR′, S—PR′, R′N—PR′, R′₂C,    R′₂Si, R′₂Ge, R′₂CCR′₂, R′₂CCR′₂CR′₂, R′₂CCR′₂CR′₂CR′₂, R′C═CR′,    R′C═CR′CR′₂, R′₂CCR′═CR′CR′₂, R′C═CR′CR′═CR′, R′C═CR′CR′₂CR′₂,    R′₂CSiR′₂, R′₂SiSiR′₂, R′₂CSiR′₂CR′₂, R′₂SiCR′₂SiR′₂, R′C═CR′SiR′₂,    R′₂CGeR′₂, R′₂GeGeR′₂, R′₂CGeR′₂CR′₂, R′₂GeCR′₂GeR′₂, R′₂SiGeR′₂,    R′C═CR′GeR′₂, R′B, R′₂C—BR′, R′₂C—BR′—CR′₂, R′₂C—O—CR′₂,    R′₂CR′₂C—O—CR′₂CR′₂, R′₂C—O—CR′₂CR′₂, R′₂C—O—CR′═CR′, R′₂C—S—CR′₂,    R′₂CR′₂C—S—CR′₂CR′₂, R′₂C—S—CR′₂CR′₂, R′₂C—S—CR′═CR′, R′₂C—Se—CR′₂,    R′₂CR′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR′═CR′, R′₂C—N═CR′,    R′₂C—NR′—CR′₂, R′₂C—NR′—CR′₂CR′₂, R′₂C—NR′—CR′═CR′,    R′₂CR′₂C—NR′—CR′₂CR′₂, R′₂C—P═CR′, and R′₂C—PR′—R′₂ where R′ is    hydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted    hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or    germylcarbyl substituent and optionally two or more adjacent R′ may    join to form a substituted or unsubstituted, saturated, partially    unsaturated or aromatic, cyclic or polycyclic substituent.-   17. The compound of any one of paragraphs 9 to 16 wherein Y is    present and is selected from CH₂, CH₂CH₂, CH(CH₃)₂, SiMe₂, SiPh₂,    SiMePh, Si(CH₂)₃, and Si(CH₂)₄, O, S, NMe, NPh, PMe, PPh, wehre Me    is methyl and Ph is phenyl.-   18. The metallocene compound of any preceding paragraphs 1 to 17    wherein the or each halogen substituent is a chloro, bromo, or iodo    substituent, preferably a chloro or bromo substituent.-   19. A metallocene compound selected from:-   bis(η⁵-2-bromo-indenyl)zirconium dichloride,-   (η⁵-2-bromoindenyl)zirconium tribromide,-   (η⁵-2-bromoindenyl)(η⁵-2-mesityl-indenyl)zirconium dibromide,-   (η⁵-2-bromoindenyl)(η⁵-2-pyrrolidinyl-indenyl)zirconium dibromide,-   (η⁵-2-bromoindenyl)(η⁵-2-(3,5-dibromophenyl)-indenyl)zirconium    dibromide,-   (η⁵-2-bromoindenyl)(η⁵-2-phenylindenyl)zirconium dibromide, and-   bis(η⁵-2-bromo-4,7-dimethyl-indenyl)zirconium dichloride.-   20. A catalyst system comprising the metallocene compound of any    preceding paragraph 1 to 19 and an activator.-   21. A process for polymerizing olefins comprising contacting the    catalyst system of paragraph 20 with at least one olefin.-   22. The process of paragraph 21 wherein said at least one olefin    comprises ethylene and/or propylene.    Experimental—Synthesis of Pre-Catalysts

All manipulations with air and moisture sensitive compounds wereperformed either in an atmosphere of thoroughly purified argon using astandard Schlenk technique or in a controlled atmosphere Glove Box(VAC). Tetrahydrofuran and diethyl ether for synthesis were purified bydistillation over LiAlH₄ and kept over sodium benzophenone ketyl.Hydrocarbon solvents (including benzene-d₆, Cambridge IsotopeLaboratories, for NMR measurements) were distilled and stored over CaH₂or Na/K alloy. Methylene chloride (and CCl₂D₂, Cambridge IsotopeLaboratories, for NMR measurements) was distilled and stored over CaH₂.Chloroform-d was distilled over P₄O₁₀ and stored over molecular sheves(3 Å). Anhydrous ZrCl₄ (Aldrich), ZrCl₄(THF)₂ (Aldrich), ^(n)BuLi inhexanes (Chemetall), anhydrous K₂CO₃ (Merck), anhydrous Na₂SO₄ (AkzoNobel), para-toluenesulfonic acid (Aldrich), bromotrimethylsilane(Aldrich), 1,3,5-tribromobenzene (Acros), indanone-2 (Aldrich),pyrrolidine (Acros), Pd(dba)₂ (Strem), tetrakis(dimethylamino)zirconium(Aldrich), tri(tert-butyl)phosphine (Strem), Silica Gel 60, 40-63 μm(Merck and Fluka) were used as obtained. Celite 503 (Fluka) was dried invacuum at 180° C. Molecular sieves 4 A (Merck) were dried in vacuum at250° C.

2-Bromo-1H-indene [(a) MacDowell, D. W. H.; Lindley, W. A. J. Org. Chem.1982, 47, 705. (b) McEwen, I.; Ronnqvist, M.; Ahlberg, P. J. Am. Chem.Soc. 1993, 115, 3989. (c) Halterman, R. L.; Fahey, D. R.; Bailly, E. F.;Dockter, D. W.; Stenzel, O.; Shipman, J. L.; Khan, M. A.; Dechert, S.;Schumann, H. Organometallics 2000, 19, 5464.], 2-phenyl-1H-indene[Sosnovskii, G. M.; Lugovskii, A. P.; Tishchenko, I. G. Z. Org. Khim.(Rus.) 1983, 19, 2143.], and 2-bromo-4,7-dimethyl-1H-indene [Halterman,R. L.; Fahey, D. R.; Bailly, E. F.; Dockter, D. W.; Stenzel, O.;Shipman, J. L.; Khan, M. A.; Dechert, S.; Schumann, H. Organometallics2000, 19, 5464.] were prepared according to the published methods.

Analytical and semi-preparative liquid chromatography was performedusing Waters Delta 600 HPLC system including 996 Photodiode ArrayDetector, Nova-Pack C18 or HR Silica (60 A, 6 μm, 3.9 and 19×300 mm) andSymmetry C18 (5 μm, 4.6×250 mm) columns. ¹H and ¹³C spectra wererecorded with a Bruker DPX-300 for 1-10% solutions in deuteratedsolvents. Chemical shifts for ¹H and ¹³C were measured relatively toTMS. C, H microanalyses were done using CHN—O-Rapid analyzer (Heracus).

EXAMPLE 1 Synthesis of bis(η⁵-2-bromo-indenyl)zirconium dichloride (1)Bis(η⁵-2-bromo-indenyl)zirconium dichloride (1)

In the Glove Box, 32.0 ml of 1.6 M ^(n)BuLi (51.2 mmol) in hexanes wereadded dropwise for 10 min at −30° C. to a solution of 10.0 g (51.3 mmol)of 2-bromoindene in 220 ml of hexanes. This mixture was stirred for 20 hat ambient temperature. The precipitate that formed was filtered off,washed with 3×50 ml of hexanes, and dried in vacuum. This procedure gave7.92 g (77%, 39.4 mmol) of the lithium salt of 2-bromoindene, which wasthen added at −100° C. to a suspension of 4.59 g (19.7 mmol) of ZrCl₄ in200 ml of CH₂Cl₂. The reaction mixture was slowly warmed for 1 h to 20°C. and, then, stirred for 24 h at ambient temperature. The resultingmixture was filtered through Celite 503 and the filtrate was evaporatedto about 70 ml. Crystals that precipitated at −30° C. were separated,washed with 3×20 ml of cold hexanes, and dried in vacuum. Yield 11.2 g(52%) of a yellow crystalline product.

Anal. calc. for C₁₈H₁₂Br₂Cl₂Zr: C, 39.29; H, 2.20. Found: C, 39.67; H,2.39.

¹H NMR (CD₂Cl₂): δ 7.46 (dd, J=6.6 Hz, J=3.2 Hz, 4H, 4,4′,7,7′-H), 7.19(dd, J=6.6 Hz, J=3.2 Hz, 4H, 5,5′,6,6′-H), 6.48 (s, 4H, 1,1′,3,3′-H).

¹³C NMR (CD₂Cl₂): δ 128.4, 127.8, 125.9, 110.1, 107.4.

EXAMPLE 2 Synthesis of (η⁵-2-bromoindenyl)zirconium tribromide (2)(η⁵-2-Bromoindenyl)zirconium tribromide (2)

To a solution of 9.49 g (48.7 mmol) of 2-bromo-1H-indene in 490 ml ofether, 12.3 g (46.3 mmol) of Zr(NMe₂)₄ was added. The reaction mixturewas stirred for 12 h and then evaporated to dryness. The residue wasdissolved in 500 ml of toluene, and 23.1 g (151 mmol) ofbromotrimethylsilane was added. The mixture was stirred for 24 h at roomtemperature, evaporated to a volume equal to ca. 250 ml, and filteredthrough a glass frit (G4). Crystals that precipitated at a temperatureof 30° C. from the filtrate were separated, washed with 3×20 ml of colddichloromethane, and dried in vacuum. Yield 16.1 g (66%) of yellowcrystalline product.

Anal. calc. for C₉H₆Br₄Zr: C, 20.59; H, 1.15. Found: C, 20.68; H, 1.20.

¹H NMR (CDCl₃): δ 7.75 (dd, 2H, J=6.5 Hz, J=3.0 Hz, 5,6-H), 7.43 (dd,J=6.5 Hz, J=3.0 Hz, 2H, 4,7-H), 7.13 (s, 2H, 1,3-H).

EXAMPLE 3 Synthesis of(η⁵-2-bromoindenyl)(η⁵-2-mesityl-indenyl)zirconium dibromide (3)2-Mesityl-1H-indene

A mixture of 50.0 ml (20.0 mmol) of 0.4 M mesitylmagnesium bromide inTHF, 230 mg (0.40 mmol) of Pd(dba)₂, 162 mg (0.80 mmol) of P^(t)Bu₃, and3.90 g (20.0 mmol) of 2-bromo-1H-indene was stirred for 48 h at ambienttemperature. Then, to the resulting mixture 200 ml of brine was added.The organic layer was separated, and the aqueous layer was extractedwith 3×100 ml of ether. The combined organic fractions were dried overK₂CO₃ and then evaporated to dryness. The product was isolated by flashchromatography on Silica Gel 60 (40-63 um, d 30 mm, 1 300 mm, eluent:hexanes-dichloromethane, 20:1, vol.). Yield 3.19 g (68%) of white solid.

Anal. calc. for C₁₈H₁₈: C, 92.26; H, 7.74. Found: C, 92.33; H, 7.73.

¹H NMR (CDCl₃): δ 7.52 (m, 1H, 7-H in indenyl), 7.46 (m, 1H, 4-H inindenyl), 7.35 (m, 1H, 6-H in indenyl), 7.24 (m, 1H, 5-H in indenyl),6.97 (s, 2H, 3,5-H in mesityl), 6.68 (m, 1H, 3-H in indenyl), 3.60 (m,2H, CH₂), 2.36 (s, 3H, 4-Me in mesityl), 2.22 (s, 6H, 2,6-Me inmesityl).

(η⁵-2-Mesitylindenyl)zirconium tribromide

To a suspension of 5.37 g (22.9 mmol) of 2-mesityl-1H-indene in 300 mlof ether 5.89 g (22.0 mmol) of Zr(NMe₂)₄ was added at room temperature.This mixture was stirred for 12 h at this temperature and thenevaporated to dryness in vacuum. To the residue dissolved in 200 ml oftoluene, 11.4 g (74.5 mmol) of trimethylbromosilane was added. Theresulting mixture was stirred for 12 h at room temperature and thenevaporated to dryness. To this residue, 30 ml of toluene and 50 ml ofhexanes were added. The precipitate formed was filtered off (using aglass frit G4) and dried in vacuum. Yield 8.98 g (64%) of yellowishpowder.

Anal. calc. for C_(21.5)H₂₁Br₃Zr: C, 42.31; H, 3.47. Found: C, 38.17; H,3.29.

¹H NMR (CD₂Cl₂): δ 7.89 (dd, 2H, J=6.6 Hz, J=3.1 Hz, 5,6-H), 7.41 (dd,J=6.6 Hz, J=3.1 Hz, 2H, 4,7-H), 7.16-7.27 (m, 2.5H, C₆H₅Me), 7.15 (s,2H, 3,5-H in Me₃C₆H₂), 7.00 (s, 2H, 1,3-H in indenyl), 2.51 (s, 6H, 2-Meand 6-Me in Me₃C₆H₂), 2.36 (s, 1.5H, C₆H5Me), 2.33 (s, 3H, 4-Me inMe₃C₆H₂).

¹³C NMR (CD₂Cl₂): δ 144.4, 140.6, 139.5, 138.2, 131.9, 131.6, 130.5,130.3, 129.7, 129.2, 128.1, 126.8, 111.0, 25.9, 22.7, 22.2.(η⁵-2-bromoindenyl)(η⁵-2-mesityl-indenyl)zirconium dibromide (3)

To a suspension of 1.08 g (1.77 mmol) of (η⁵-2-mesitylindene)zirconiumtribromide in 36 ml of a 1:1 mixture of toluene-ether, 356 mg (1.77mmol) of lithium salt of 2-bromo-1H-indene was added at −30° C. Thismixture was stirred for 24 h at room temperature and then evaporated todryness. The residue was dissolved in 50 ml of toluene. The resultingmixture was stirred for 2 h at 80° C. and then filtered through Celite503. The Celite layer was additionally washed with 3×10 ml of hottoluene. The combined filtrate was evaporated to dryness, and theresidue washed with 4×10 ml of hexanes and dried in vacuum. Yield 0.50 g(42%) of yellowish powder.

Anal. calc. for C₂₇H₂₃Br₃Zr: C, 47.80; H, 3.42. Found: C, 47.62; H,3.30.

¹H NMR (CDCl₃): δ 7.60 (dd, J=6.4 Hz, J=3.1 Hz, 2H, 4,7-H in(2,4,6-trimethylphenyl)indenyl), 7.26 (m, 6H, 5,6-H in(2,4,6-trimethylphenyl)indenyl and 4,5,6,7-H in 2-bromoindenyl), 7.09(s, 2H, 3,5-H in Me₃C₆H₂), 6.36 (s, 2H, 1,3-H in2,4,6-trimethylphenyl)indenyl), 6.02 (s, 2H, 1,3-H in 2-bromoindenyl).

EXAMPLE 4

Synthesis of (η⁵-2-bromoindenyl)(η⁵-2-pyrrolidinyl-indenyl)zirconiumdibromide (4) 1-(1H-Inden-2-yl)pyrrolidine

A mixture of 12.5 g (94.7 mmol) of indanone-2, 8.52 g (120 mmol) ofpyrrolidine, 30 g of activated molecular sieves (4A), and 210 ml oftoluene were stirred for 24 h at 70° C. This mixture was cooled to roomtemperature, filtered through a glass frit (G2), and the precipitate(crushed molecular shieves) was washed with 3×30 ml of hexanes. Thecombined filtrate was evaporated to dryness, and the residue wasrecrystallized from 100 ml of hot hexanes. Crystals that precipitated at0° C. were collected, washed with 2×10 ml of cold hexanes, and dried invacuum. Yield 8.40 g (48%).

Anal. calc. for C₁₃H₁₅N: C, 84.28; H, 8.16. Found: C, 84.11; H, 8.21.

¹H NMR (CDCl₃): δ 7.20 (d, J=7.3 Hz, 1H, 7-H), 7.10 (t, J=7.3 Hz, 1H,6-H), 7.00 (d, J=7.3 Hz, 1H, 4-H), 6.81 (t, J=7.3 Hz, 1H, 5-H), 5.21(br.s., 1H, 3-H), 3.39 (s, 2H, 1-H), 3.25 (m, 4H, 2,2′,5,5′-H inpyrrolidinyl), 1.97 (m, 4H, 3,3′,4,4′-H in pyrrolidinyl).

(η⁵-2-bromoindenyl)(η⁵-2-pyrrolidinyl-indenyl)zirconium dibromide (4)

To a solution of 0.53 g (2.86 mmol) of 1-(1H-inden-2-yl)pyrrolidine in25 ml of ether, 1.14 ml (2.86 mmol) of 2.5 M ^(n)BuLi in hexanes wasadded at room temperature. This mixture was stirred for 12 h and thenadded to a suspension of 1.63 g (2.86 mmol) of(η⁵-2-bromoindenyl)zirconium tribromide in 60 ml of a mixture oftoluene-ether (1:1, vol.) at −30° C. The resulting mixture was stirredfor 24 h at room temperature and then it was evaporated to dryness. Theresidue was dissolved in 80 ml of toluene; the mixture stirred for 2 hat 100° C. and then filtered through Celite 503. The Celite layer wasadditionally washed with 2×20 ml of hot toluene. The combined filtratewas evaporated to dryness, and the residue was recrystallized from 15 mlof hot toluene. Crystals that precipitated at 0° C. were collected,washed with 5 ml of cold toluene, and dried in vacuum. Yield 0.80 g(44%) of yellowish crystalline solid.

Anal. calc. for C₂₂H₂₀Br₃NZr: C, 41.99; H, 3.20. Found: C, 41.78; H,3.05.

¹H NMR (C₆D₆): δ 7.42 (dd, J=6.3 Hz, J=3.0 Hz, 2H, 4,7-H in2-bromoindenyl), 7.02 (dd, J=6.3 Hz, J=3.0 Hz, 2H, 4,7-H in2-pyrrolidinylindenyl), 6.84 (dd, J=6.3 Hz, J=3.0 Hz, 4H, 5,6,5′,6′-H),6.04 (s, 2H, 1,3-H in 2-bromoindenyl), 5.18 (s, 2H, 1,3-H in2-pyrrolidinylindenyl), 3.26 (m, 2H, 2,5-H in pyrrolidinyl), 2.70 (m,2H, 2′,5′-H in pyrrolidinyl), 1.66 (m, 2H, 3,4-H in pyrrolidinyl), 1.39(m, 2H, 3′,4′-H in pyrrolidinyl).

EXAMPLE 5 Synthesis of(η⁵-2-bromoindenyl)(η⁵-2-(3,5-dibromophenyl)-indenyl)zirconium dibromide(5) 2-(3,5-Dibromophenyl)-1H-indene

To a solution of 12.6 g (40.0 mmol) of 1,3,5-tribromobenzene in 400 mlof ether, 160 ml (40.0 mmol) of 0.25 M ^(n)BuLi in hexanes was added for1 h at −80° C. The mixture was stirred for 1.5 h at this temperature,and then a solution of 5.29 g (40.0 mmol) of indanone-2 in 200 ml ofether was added dropwise over 1 hour while vigorously stirring. Thereaction mixture was allowed to warm to room temperature and it wasstirred at this temperature for 24 h. Then, 100 ml of water was added.The organic layer was separated; the aqueous layer was extracted with3×50 ml of dichloromethane. The combined organic layers were dried overNa₂SO₄ and then evaporated to dryness. The residue was dissolved in 250ml of toluene, and 0.75 g of p-TosOH was added. The resulting solutionwas refluxed for 1 hours using a Dean-Stark trap to remove the waterformed. Next, the mixture was evaporated to dryness, and the product wasisolated by flash-chromatography on Silica Gel 60 (d 50 mm, 1 400 mm,eluent: hexanes). Yield 8.54 g (61%) of white powder.

Anal. calc. for C₁₅H₁₀Br₂: C, 51.47; H, 2.88. Found: C, 51.66; H, 2.80.

¹H NMR (CDCl₃): δ 7.60 (d, 2H, J=1.5 Hz, 2,6-H in Br₂C₆H₃), 7.49 (m, 1H,4-H in Br₂C₆H₃), 7.43 (d, J=7.3 Hz, 1H, 7-H in indenyl), 7.38 (d, J=7.3Hz, 1H, 4-H in indenyl), 7.27 (t, J=7.3 Hz, 1H, 5-H in indenyl), 7.20(t, J=7.3 Hz, 1H, 6-H in indenyl), 7.18 (m, 1H, 3-H in indenyl), 3.63(br.s., 1H, 1-H in indenyl).

¹³C NMR (CDCl₃): δ 144.4, 143.1, 143.0, 139.4, 132.4, 129.1, 127.2,126.8, 125.6, 123.7, 123.2, 121.5, 38.8.

(η⁵-2-bromoindenyl)(η⁵-2-(3,5-dibromophenyl)-indenyl)zirconium dibromide(5)

To a suspension of 1.08 g (1.90 mmol) of (η⁵-2-bromoindenyl)zirconiumtribromide in 40 ml of a mixture of toluene-ether (1:1, vol.), 0.71 g(1.90 mmol) of the sodium salt of 2-(3,5-dibromophenyl)-1H-indene wasadded at −30° C. This mixture was stirred for 48 h at room temperatureand then it was evaporated to dryness. To the residue, 40 ml of toluenewas added. The resulting mixture was stirred for 5 h at 70° C. and thenfiltered through Celite 503. The Celite layer was additionally washedwith 3×10 ml of hot toluene. The combined filtrate was evaporated todryness, and the residue was recrystallized from 30 ml of hot toluene.Crystals that precipitated at room temperature were collected, washedwith 2×5 ml of cold toluene, and dried in vacuum. Yield 0.85 g (56%) ofyellowish crystalline solid.

Anal. calc. for C₂₄H₁₅Br₅Zr: C, 36.30; H, 1.90. Found: C, 36.47; H,2,04.

¹H NMR (C₆D₆): δ 7.59 (d, J=1.7 Hz, 2H, 2,6-H in Br₂C₆H₃), 7.42 (t,J=1.7 Hz, 1H, 4-H in Br₂C₆H₃), 7.31 (dd, J=6.6 Hz, J=3.1 Hz, 2H, 4,7-Hin 2-dibromophenyl)indenyl), 6.92 (dd, J=6.3 Hz, J=3.1 Hz, 2H, 4,7-H in2-bromoindenyl), 6.81 (m, 4H, 5,6-H in 2-(3,5-dibromophenyl)indenyl and5,6-H in 2-bromoindenyl), 6.27 (m, 2H, 1,3-H in2-(3,5-dibromophenyl)indenyl, 5.92 (m, 2H, 1,3-H in 2-bromoindenyl).

¹³C NMR (C₆D₆): δ 134.0, 129.3, 128.7, 128.2, 128.0, 127.9, 127.8,127.1, 126.7, 125.9, 124.8, 123.4, 109.2, 103.8.

EXAMPLE 6 Synthesis of (η⁵-2-bromoindenyl)(η⁵-2-phenylindenyl)zirconiumdibromide (6)

To a suspension of 0.55 g (2.86 mmol) of 2-phenyl-1H-indene in a mixtureof toluene-ether (1/1, vol.), 1.14 ml (2.86 mmol) of 2.5 M ^(n)BuLi inhexanes was added at −30° C. This mixture was stirred for 24 h at roomtemperature, then cooled to −30° C., and 1.63 g (2.86 mmol) of(η⁵-2-bromoindenyl)zirconium tribromide was added. The resulting mixturewas stirred for 24 h at room temperature and then evaporated to dryness.The residue was dissolved in 50 ml of toluene, and this mixture wasstirred for 5 h at 100° C., and then filtered through Celite 503. Thefiltrate was evaporated to dryness under vacuum. The residue wasrecrystallized from 15 ml of hot toluene. Crystals that precipitated atambient temperature were collected, washed with 2×3 ml of cold toluene,and dried in vacuum. Yield 900 mg (49%) of yellowish crystalline solid.

Anal. calc. for C₂₄H₁₇Br₃Zr: C, 45.30; H, 2.69. Found: C, 45.42; H,2.80.

¹H NMR (CD₂Cl₂): δ 7.74 (m, 2H, 4,7-H in 2-phenylindenyl), 7.61 (dd,J=6.3 Hz, J=3.0 Hz, 2H, 5,6-H in 2-phenylindenyl), 7.52 (m, 2H, 4,7-H in2-bromindenyl), 7.43 (tt, J=7.6 Hz, J=1.2 Hz, 1H, 4-H in Ph), 7.28 (dd,J=6.4 Hz, J=2.8 Hz, 2H, 5,6-H in 2-bromindenyl), 7.1 (m, 4H, 2,3,5,6-Hin Ph), 7.03 (s, 2H, 1,3-H in 2-phenylindenyl), 6.35 (s, 2H, 1,3-H in2-bromindenyl).

¹³C NMR (CD₂Cl₂): δ 135.0, 134.4, 130.7, 130.6, 129.7, 128.9, 128.6,128.3, 127.5, 127.2, 126.4, 126.0, 111.1, 105.5.

EXAMPLE 7 Synthesis of bis(η⁵-2-bromo-4,7-dimethyl-indenyl)zirconiumdichloride (7)

To a solution of 10.0 g (44.8 mmol) of 2-bromo-4,7-dimethyl-1H-indene in200 ml of hexanes, 17.9 ml (44.8 mmol) of 2.5 M ^(n)BuLi in hexanes wasadded. The reaction mixture was stirred for 12 h at room temperature,and then the precipitate formed was filtered off using a glass frit (G3)funnel and dried in vacuum. This procedure gave 8.60 g (84%) of thelithium salt of 2-bromo-4,7-dimethyl-1H-indene. Next, to a suspension of7.08 g (18.8 mmol) of ZrCl₄(THF)₂ in 200 ml of dichloromethane, 8.60 g(37.5 mmol) of the above-obtained lithium salt was added. The resultingmixture was stirred for 24 h and then filtered through a glass frit(G4). The precipitate was additionally washed with 3×30 ml ofdichloromethane. The combined filtrate was evaporated to dryness. Theresidue was recrystallized from 100 ml of dichloromethane. Crystals thatprecipitated at −30° C. were collected, washed with 3×50 ml of hexanes,and dried in vacuum. Yield 2.80 g (25%).

Anal. calc. for C₂₂H₂₀Br₂Cl₂Zr: C, 43.58; H, 3.32 Found: C, 43.40; H,3.23.

¹H NMR (CD₂Cl₂): δ 6.87 (m, 4H, 5,5′,6,6′-H), 6.65 (s, 4H, 1,1′,3,3′-H),2.35 (s, 12H, 4,4′,7,7′-CH₃).

Experimental—Polymerizations

In the following experiments pressure is reported in atmospheres (atm)and pounds per square inch (psi). The conversion factors to S. I. Unitsare: 1 psi equals 6.894757 kPa and 1 atm equals 101.325 kPa.

Transition metal compound (TMC) solutions were typically prepared usingtoluene (ExxonMobil Chemical—anhydrous, stored under N₂) (98%). Unlessotherwise mentioned, TMC solutions are 0.2 mmol/L for C₂ and C₂/C₈(co)polymerizations.

Solvents, polymerization grade toluene and hexanes were supplied byExxonMobil Chemical Co. and thoroughly dried and degassed prior to use.

1-octene (98%) was purchased from Aldrich Chemical Company and dried bystirring over NaK overnight followed by filtration through basic alumina(Aldrich Chemical Company, Brockman Basic 1).

Polymerization grade ethylene was used and further purified by passingit through a series of columns: 500 cc Oxyclear cylinder from Labclear(Oakland, Calif.) followed by a 500 cc column packed with dried 3 Å molesieves purchased from Aldrich Chemical Company, and a 500 cc columnpacked with dried 5 Å mole sieves purchased from Aldrich ChemicalCompany.

MAO (methylalumoxane, 10 wt % in toluene) was purchased from AlbemarleCorporation and was used as a 1 wt % in toluene solution. Micromoles ofMAO reported in the experimental section are based on the micromoles ofaluminum in MAO. The formula weight of MAO is 58.0 grams/mole. TiBAl(triisobutylaluminum, NEAT) and TnOAl (tri-n-octylaluminum, NEAT) werepurchased from AKZO Nobel. TnOAl was used as a 0.01 mol/L solution inhexanes, and TiBAl was used as a 5 mmol/L solution in toluene.Dimethylanilinium tetrakis(perfluorophenyl)borate ([DMAH][B(PfP)₄],[PhNMe₂H][B(C₆F₅)₄], D4) was purchased from Albemarle Corporation orBoulder Scientific Company and used without further purification.

Reactor Description and Preparation:

Polymerizations were conducted in an inert atmosphere (N2) drybox usingautoclaves equipped with an external heater for temperature control,glass inserts (internal volume of reactor=23.5 mL for C2 and C2/C8runs), septum inlets, regulated supply of nitrogen, ethylene andpropylene, and equipped with disposable PEEK mechanical stirrers (800RPM). The autoclaves were prepared by purging with dry nitrogen at 110°C. or 115° C. for 5 hours and then at 25° C. for 5 hours.

Ethylene Polymerization or Ethylene/1-Octene Copolymerization:

The reactor was prepared as described above, and then purged withethylene. Toluene, 1-octene (100 μL when used), scavenger (1.0 μmolTnOAl, used only when D4 was used, 10 mmol/L in hexane), and activator(MAO or D4) were added via syringe at room temperature and atmosphericpressure. The reactor was then brought to process temperature (80° C.)and charged with ethylene to process pressure (75 psig=618.5 kPa) whilestirring at 800 RPM. The transition metal compound (TMC, 0.02 μmol) wasadded via syringe with the reactor at process conditions. In cases wheresome MAO (0.4 μmol of Al) or TIBAL (0.08 μmol, 5 mmol/L in toluene) wasalso precontacted with the TMC, the MAO or TIBAL was added to the TMCfirst and then the resulting solution was added to the reactor atprocess conditions. Amounts of reagents not specified above are given inTables 1 and 3. Ethylene was allowed to enter (through the use ofcomputer controlled solenoid valves) the autoclaves duringpolymerization to maintain reactor gauge pressure (±2 psig). Reactortemperature was monitored and typically maintained within ±1° C.Polymerizations were halted by addition of approximately 50 psi O2/Ar (5mole % O2) gas mixture to the autoclaves for approximately 30 seconds.The polymerizations were quenched after a predetermined cumulativeamount of ethylene had been added or for a maximum of 20 minutespolymerization time. The final conversion (in psi) of ethyleneadded/consumed is reported in the Tables 1 and 3, in addition to thequench time for each run. The reactors were cooled and vented. Thepolymer was isolated after the solvent was removed in-vacuo. Yieldsreported include total weight of polymer and residual catalyst. Catalystactivity is reported as grams of polymer per mmol transition metalcompound per atmosphere ethylene per hour of reaction time(g/mmol·hr·atm).

Polymer Characterization: 100217] Polymer characterization results forpolyethylene samples are reported in Table 2, for ethylene-1-octenecopolymers are reported in Table 4.

For analytical testing, polymer sample solutions were prepared bydissolving polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity fromSigma-Aldrich) containing 2,6-di-tert-butyl-4-methylphenol (BHT, 99%from Aldrich) at 160° C. in a shaker oven for approximately 3 hours. Thetypical concentration of polymer in solution is between 0.4 to 0.9 mg/mLwith a BHT concentration of 1.25 mg BHT/mL of TCB. Samples are cooled to135° C. for testing.

Molecular weights (weight average molecular weight (Mw) and numberaverage molecular weight (Mn)) and molecular weight distribution(MWD=Mw/Mn), which is also sometimes referred to as the polydispersity(PDI) of the polymer, were measured by Gel Permeation Chromatographyusing a Symyx Technology GPC equipped with evaporative light scatteringdetector and calibrated using polystyrene standards (PolymerLaboratories: Polystyrene Calibration Kit S-M-10: Mp (peak Mw) between5000 and 3,390,000). Samples were run in TCB at (135° C. sampletemperatures, 160° C. oven/columns) using three Polymer Laboratories:PLgel 10 μm Mixed-B 300×7.5 mm columns in series. No column spreadingcorrections were employed. Numerical analyses were performed usingEpoch® software available from Symyx Technologies.

The sample preparation for SAMMS (Sensory Array Modular MeasurementSystem) thermal analysis measurements involved depositing the stabilizedpolymer solution onto a silanized wafer (Part Number S10457, Symyx). Thesolvent was then evaporated off at ˜145° C. By this method,approximately between 0.12 and 0.24 mg of polymer is deposited onto eachcorresponding wafer cell. Thermal analysis was measured on a SymyxTechnologies SAMMS instrument that measures polymer melt temperaturesvia the 3ω technique. The analysis first employs a rapid-scan protocolthat heats each cell from 27° C. to 200° C. in ˜35 seconds and thenrapidly cools the sample to room temperature. This complete proceduretakes approximately 60 seconds per cell and is used to minimize eachsample's thermal history. The second step involves running ahigh-resolution scan protocol to measure the second melt of the sample.The protocol heats each cell from 27° C. to 200° C. in ˜3 minutes andthen rapidly cools the sample to room temperature. The high-resolutionscan takes approximately three times the amount of time to complete asthe rapid-scan protocol. If multiple melting peaks are present, Epoch®Software reports the largest amplitude peak. SAMMS data is reportedunder the heading of Tm (° C.) in Tables 2 and 4.

Samples for infrared analysis were prepared by depositing the stabilizedpolymer solution onto a silanized wafer (Part number S10860, Symyx). Bythis method, approximately between 0.12 and 0.24 mg of polymer isdeposited on the wafer cell. The samples were subsequently analyzed on aBrucker Equinox 55 FTIR spectrometer equipped with Pikes's MappIRspecular reflectance sample accessory. Spectra, covering a spectralrange of 5000 cm⁻¹ to 500 cm⁻¹, were collected at a 2 cm⁻¹ resolutionwith 32 scans.

For ethylene-1-octene copolymers, the wt. % copolymer is determined viameasurement of the methyl deformation band at ˜1375 cm⁻¹. The peakheight of this band is normalized by the combination and overtone bandat ˜4321 cm⁻¹, which corrects for path length differences. Thenormalized peak height is correlated to individual calibration curvesfrom ¹H NMR data to predict the wt. % copolymer content within aconcentration range of 2 to 35 wt. % for octene. Typically, R²correlations of 0.98 or greater are achieved. These numbers are reportedin Table 4 under the heading Octene wt %). TABLE 1 EthylenePolymerization Runs - Part I. Total Total Final Quench PolymerActivator^(a) Toluene Hexanes Conversion Time Yield Activity Ex # TMCActivator (μmol) (mL) (mL) (psi) (sec) (g) (g/(mmol · hr · atm)) PE-1 1MAO 10.00 5.00 0 20.1 124.5 0.0771 18,268 PE-2 1 MAO 10.00 5.00 0 20.1130.0 0.0738 16,746 PE-3 1 MAO 10.00 5.00 0 20.1 185.1 0.0782 12,461PE-4 1 MAO 10.00 5.00 0 20.3 154.0 0.0790 15,136 PE-5 1^(d) D4 0.02 4.900.099 20.1 349.6 0.0572 4,826 PE-6 1^(d) D4 0.02 4.90 0.099 20.1 96.00.0539 16,557 PE-7 1^(d) D4 0.02 4.90 0.099 20.1 171.1 0.0410 7,068 PE-81^(d) D4 0.02 4.90 0.099 20.1 121.9 0.0558 13,501^(a)Micromoles refers to the micromoles of Al in MAO.^(d)In this experiment, TiBAl was premixed with the indicated TMC.

TABLE 2 Ethylene Polymerization Runs - Part II. Ex # TMC Mw Mn PDI Tm (°C.) PE-1 1 839,200 439,031 1.9 — PE-2 1 841,340 447,738 1.9 — PE-3 1821,613 419,726 2.0 — PE-4 1 860,729 447,300 1.9 — PE-5 1 684,677340,517 2.0 — PE-6 1 676,786 365,728 1.9 — PE-7 1 719,991 396,051 1.8 —PE-8 1 740,976 391,500 1.9 —

TABLE 3 Ethylene-1-Octene Polymerization Runs - Part I. Total TotalFinal Quench Polymer Activator^(a) Toluene Hexanes Conversion Time YieldActivity Ex # TMC Activator (μmol) (mL) (mL) (psi) (sec) (g) (g/(mmol ·hr · atm)) EO-1 1 MAO 10.00 4.90 0 20.1 75.3 0.0569 22,298 EO-2 1 MAO10.00 4.90 0 20.1 88.5 0.0575 19,160 EO-3 1 MAO 10.00 4.90 0 20.1 93.00.0615 19,505 EO-4 1 MAO 10.00 4.90 0 20.3 96.0 0.0594 18,249 EO-5 1^(d)D4 0.02 4.80 0.099 20.1 151.8 0.0250 4,857 EO-6 1^(d) D4 0.02 4.80 0.09920.1 108.8 0.0416 11,279 EO-7 1^(d) D4 0.02 4.80 0.099 20.1 205.6 0.04216,041 EO-8 1^(d) D4 0.02 4.80 0.099 20.1 677.4 0.0408 1,777 EO-9 2^(b)MAO 10.00 4.90 0 3.1 1200.1 0.0123 302 EO-10 2^(b) MAO 10.00 4.90 0 3.51201.3 0.0113 211 EO-11 2^(b) MAO 10.00 4.90 0 3.4 1200.5 0.0127 312EO-12 4^(c) MAO 10.00 4.90 0 20.1 1011.8 0.0322 939 EO-13 4^(c) MAO10.00 4.90 0 20.1 1150.0 0.0274 703 EO-14 4^(c) MAO 10.00 4.90 0 20.1810.6 0.0319 1,161 EO-15 5^(b) MAO 10.00 4.90 0 20.1 223.1 0.0442 5,844EO-16 5^(b) MAO 10.00 4.90 0 20.1 472.4 0.0629 3,928 EO-17 5^(b) MAO10.00 4.90 0 20.3 212.0 0.0444 6,178 EO-18 7^(b) MAO 10.00 4.90 0 20.1330.3 0.0684 6,109 EO-19 7^(b) MAO 10.00 4.90 0 20.1 255.9 0.0685 7,896EO-20 7^(b) MAO 10.00 4.90 0 20.1 311.4 0.0711 6,735^(a)Micromoles refers to the micromoles of Al in MAO.^(b)In this experiment, an additional 20 equivalents (relative to theTMC) of MAO was premixed with the indicated TMC.^(c)In this experiment, an additional 20 equivalents (relative to theTMC) of MAO was premixed with the indicated TMC and the complex formedwas heated for 20 min using a hot plate set at 80° C.^(d)In this experiment, TiBAl was premixed with the indicated TMC.

TABLE 4 Ethylene-1-Octene Polymerization Runs - Part II. Octene Tm Ex #TMC Mw Mn PDI (wt %) (° C.) EO-1 1 791,546 431,506 1.8 5.1 — EO-2 1772,701 414,829 1.9 4.8 — EO-3 1 809,161 425,614 1.9 5.0 — EO-4 1789,787 431,932 1.8 4.9 — EO-5 1 697,076 395,779 1.8 2.4 — EO-6 1668,176 370,227 1.8 2.2 — EO-7 1 683,109 371,015 1.8 2.9 — EO-8 1659,623 289,568 2.3 2.7 — EO-9 2 1,541,892 458,766 3.4 4.3 126.3 EO-10 21,403,482 589,540 2.4 2.7 127.4 EO-11 2 1,448,878 770,470 1.9 3.1 128.2EO-12 4 903,208 323,364 2.8 2.3 127.2 EO-13 4 922,531 371,483 2.5 2.2127.2 EO-14 4 930,088 331,643 2.8 2.3 127.5 EO-15 5 804,553 437,627 1.83.9 121.4 EO-16 5 814,647 438,906 1.9 3.8 122.4 EO-17 5 845,833 477,6661.8 3.9 121.4 EO-18 7 981,925 512,305 1.9 4.1 122.4 EO-19 7 952,584497,202 1.9 4.3 122.3 EO-20 7 971,157 497,833 2.0 4.1 123.5

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For this reason, then, reference shouldbe made solely to the appended claims for purposes of determining thetrue scope of the present invention. All documents described herein areincorporated by reference herein, including any priority documentsand/or testing procedures to the extent they are not inconsistent withthis text. Likewise, the term “comprising” is considered synonymous withthe term “including” for purposes of Australian law.

1. A metallocene compound comprising a transition metal and at least onesubstituted monocyclic or polycyclic arene ligand bonded to thetransition metal, wherein said arene ligand comprises at least onehalogen substituent directly bonded to an sp² carbon atom at a bondablering position of an aromatic five-membered ring of said arene ligand. 2.The metallocene compound of claim 1 and including a second monoanionicligand bonded to the transition metal.
 3. A metallocene compoundcomprising a transition metal, a first substituted indenyl ligandpi-bonded to the transition metal, and a second monoanionic ligandbonded to the transition metal, wherein said first ligand comprises atleast one halogen substituent directly bonded to an sp² carbon atom atthe one, two or three position of the indenyl ligand.
 4. The metallocenecompound of claim 3 wherein said second monoanionic ligand is asubstituted or unsubstituted monocyclic or polycyclic ligand pi-bondedto the transition metal.
 5. The metallocene compound of claim 3 whereinsaid second monoanionic ligand is a substituted or unsubstitutedmonocyclic or polycyclic arene ligand pi-bonded to the transition metal.6. The metallocene compound of claim 3 wherein said second monoanionicligand is a substituted or unsubstituted indenyl ligand or a substitutedor unsubstituted fluorenyl ligand.
 7. The metallocene compound of claim3 wherein the transition metal is from a Group 3, 4, 5 or 6 of thePeriodic Table of Elements, or a lanthanide metal or an actinide metal.8. The metallocene compound of claim 3 wherein the transition metal is aGroup 4 transition metal selected from titanium, zirconium and hafnium.9. The metallocene compound of claim 3 wherein said at least one halogensubstituent is a chloro, bromo, or iodo substituent.
 10. The metallocenecompound of claim 3 wherein said at least one halogen substituent is achloro or bromo substituent.
 11. A metallocene compound comprising atransition metal, a first substituted fluorenyl ligand pi-bonded to thetransition metal, a second monoanionic ligand bonded to the transitionmetal, wherein said first ligand comprises at least one halogensubstituent directly bonded to an sp² carbon atom at the nine positionof the fluorenyl ligand.
 12. The metallocene compound of claim 11wherein said second monoanionic ligand is a substituted or unsubstitutedmonocyclic or polycyclic ligand pi-bonded to the transition metal. 13.The metallocene compound of claim 11 wherein said second monoanionicligand is a substituted or unsubstituted monocyclic or polycyclic areneligand pi-bonded to the transition metal.
 14. The metallocene compoundof claim 11 wherein said second monoanionic ligand is a substituted orunsubstituted indenyl ligand or a substituted or unsubstituted fluorenylligand.
 15. The metallocene compound of claim 11 wherein the transitionmetal is from a Group 3, 4, 5 or 6 of the Periodic Table of Elements, ora lanthanide metal or an actinide metal.
 16. The metallocene compound ofclaim 11 wherein the transition metal is a Group 4 transition metalselected from titanium, zirconium and hafnium.
 17. The metallocenecompound of claim 11 wherein said at least one halogen substituent is achloro, bromo, or iodo substituent.
 18. The metallocene compound ofclaim 11 wherein said at least one halogen substituent is a chloro orbromo substituent.
 19. A metallocene compound represented by the formula(1):

wherein M is a Group 3, 4, 5 or 6 transition metal atom, or a lanthanidemetal atom, or actinide metal atom; E is a substituted polycyclic areneligand pi-bonded to M and including at least one halogen substituentdirectly bonded to an sp² carbon atom at a bondable ring position of anaromatic five-membered ring of said arene ligand; A is a monanionicligand bonded to M; Y is bonded to A and to any single bondable positionof the ring structure of E, and is a bridging group containing a Group13, 14, 15, or 16 element, and is present when y is one and absent wheny is zero; y is zero or one; and each X is a univalent anionic ligand,or two X are joined and bound to the metal atom to form a metallocyclering, or two X are joined to form a chelating ligand, a diene ligand, oran alkylidene ligand.
 20. The metallocene compound of claim 19 wherein Eis a substituted indenyl ligand and said at least one halogensubstituent is connected to the one, two or three position of theindenyl ligand.
 21. The metallocene compound of claim 19 wherein E is asubstituted fluorenyl ligand and said at least one halogen substituentis connected to the nine position of the fluorenyl ligand.
 22. Themetallocene compound of claim 19 wherein A is a substituted orunsubstituted monocyclic or polycyclic ligand pi-bonded to M.
 23. Themetallocene compound of claim 19 wherein A is a substituted orunsubstituted monocyclic or polycyclic arene ligand pi-bonded to M. 24.The metallocene compound of claim 19 wherein A is a substituted orunsubstituted indenyl ligand or fluorenyl ligand.
 25. The metallocenecompound of claim 19 wherein M is a Group 4 transition metal selectedfrom titanium, zirconium and hafnium.
 26. The metallocene compound ofclaim 19 wherein said at least one halogen substituent is a chloro,bromo, or iodo substituent.
 27. The metallocene compound of claim 19wherein said at least one halogen substituent is a chloro or bromosubstituent.
 28. The compound of claim 19 wherein Y is present and is abridging group containing boron or a Group 14, 15 or 16 element.
 29. Thecompound of claim 19 wherein Y is present and is selected from the groupconsisting of: S, O, NR′, PR′, AsR′, SbR′, O—O, S—S, R′N—NR′, R′P—PR′,O—S, O—NR′, O—PR′, S—NR′, S—PR′, R′N—PR′, R′₂C, R′₂Si, R′₂Ge, R′₂CCR′₂,R′₂CCR′₂CR′₂, R′₂CCR′₂CR′₂CR′₂, R′C═CR′, R′C═CR′CR′₂, R′₂CCR′═CR′CR′₂,R′C═CR′CR′═CR′, R′C═CR′CR′₂CR′₂, R′₂CSiR′₂, R′₂SiSiR′₂, R′₂CSiR′₂CR′₂,R′₂SiCR′₂SiR′₂, R′C═CR′SiR′₂, R′₂CGeR′₂, R′₂GeGeR′₂, R′₂CGeR′₂CR′₂,R′₂GeCR′₂GeR′₂, R′₂SiGeR′₂, R′C═CR′GeR′₂, R′B, R′₂C—BR′, R′₂C—BR′—CR′₂,R′₂C—O—R′₂, R′₂CR′₂C—O—CR′₂CR′₂, R′₂C—O—CR′₂CR′₂, R′₂C—O—CR′═CR′,R′₂C—S—CR′₂, R′₂CR′₂C—S—CR′₂CR′₂, R′₂C—S—CR′₂CR′₂, R′₂C—S—CR′═CR′,R′₂C—Se—CR′₂, R′₂CR′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR′═CR′,R′₂C—N═CR′, R′₂C—NR′—CR′₂, R′₂C—NR′—CR′₂CR′₂, R′₂C—NR′—CR′═CR′,R′₂CR′₂C—NR′—CR′₂CR′₂, R′₂C—P═CR′, and R′₂C—PR′—CR′₂ where R′ ishydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbylsubstituent and optionally two or more adjacent R′ may join to form asubstituted or unsubstituted, saturated, partially unsaturated oraromatic, cyclic or polycyclic substituent.
 30. The compound of claim 19wherein Y is present and is selected from CH₂, CH₂CH₂, CH(CH₃)₂, SiMe₂,SiPh₂, SiMePh, Si(CH₂)₃, and Si(CH₂)₄, O, S, NMe, NPh, PMe, PPh, whereMe is methyl nad Ph is phenyl.
 31. A metallocene compound represented bythe formula (2):

wherein M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanidemetal atom, or actinide metal atom; R¹, R², R³, R⁴, R⁵, R⁶, and R⁷ are,independently, hydrogen, or a hydrocarbyl, substituted hydrocarbyl,halogen, halocarbyl, substituted halocarbyl, silylcarbyl, substitutedsilylcarbyl, germylcarbyl, substituted germylcarbyl, or other heteroatomsubstituents wherein the heteroatom is bonded directly to a ring carbonatom of the indenyl ligand and is boron, a Group 14 atom that is notcarbon, a Group 15 atom, or a Group 16 atom, and adjacent R¹, R², R³,R⁴, R⁵, R⁶, and R⁷ may be joined together to form a substituted orunsubstituted, saturated, partially unsaturated, or aromatic cyclic orpolycyclic substituent; Y is an optional bridging group that contains aGroup 13, 14, 15, or 16 element, and that is bonded to A and to anysingle bondable position of the indenyl ligand, and is present when y isone and absent when y is zero, and when present, Y replaces one of R¹,R², R³, R⁴, R⁵, R⁶, and R⁷ in formula (2); y is zero or one; A is asubstituted or unsubstituted cyclopentadienyl ligand, a substituted orunsubstituted indenyl ligand, or a substituted or unsubstitutedfluorenyl ligand; and each X is a univalent anionic ligand, or two X arejoined and bound to the metal atom to form a metallocycle ring, or two Xare joined to form a chelating ligand, a diene ligand, or an alkylideneligand; provided that at least one of R₁, R₂ and R₃ is a halogensubstituent,
 32. The metallocene compound of claim 31 wherein saidhalogen substituent is a chloro, bromo or iodo substituent.
 33. Themetallocene compound of claim 31 wherein said halogen substituent is achloro or bromo substituent.
 34. The compound of claim 31 wherein Y ispresent and is a bridging group containing boron or a Group 14, 15 or 16element.
 35. The compound of claim 31 wherein Y is present and isselected from the group consisting of: S, O, NR′, PR′, AsR′, SbR′, O—O,S—S, R′N—NR′, R′P—PR′, O—S, O—NR′, O—PR′, S—NR′, S—PR′, R′N—PR′, R′₂C,R′₂Si, R′₂Ge, R′₂CCR′₂, R′₂CCR′₂CR′₂, R′₂CCR′₂CR′₂CR′₂, R′C═CR′,R′C═CR′CR′₂, R′₂CCR′═CR′CR′₂, R′C═CR′CR′═CR′, R′C═CR′CR′₂CR′₂,R′₂CSiR′₂, R′₂SiSiR′₂, R′₂CSiR′₂CR′₂, R′₂SiCR′₂SiR′₂, R′C═CR′SiR′₂,R′₂CGeR′₂, R′₂GeGeR′₂, R′₂CGeR′₂CR′₂, R′₂GeCR′₂GeR′₂, R′₂SiGeR′₂,R′C═CR′GeR′₂, R′B, R′₂C—BR′, R′₂C—BR′—CR′₂, R′₂C—O—CR′₂,R′₂CR′₂CCR′₂CR′₂, R′₂C—O—CR′₂CR′₂, R′₂C—O—CR′═CR′, R′₂C—S—CR′₂,R′₂CR′₂C—S—CR′₂CR′₂, R′₂C—S—CR′₂CR′₂, R′₂C—S—CR′═CR′, R′₂C—Se—CR′₂,R′₂CR′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR′═CR′, R′₂C—N═CR′,R′₂C—NR′—CR′₂, R′₂C—NR′—CR′₂CR′₂, R′₂C—NR′—CR′═CR′,R′₂CR′₂C—NR′—CR′₂CR′₂, R′₂C—P═CR′, and R′₂C—PR′—CR′₂ where R′ ishydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbylsubstituent and optionally two or more adjacent R′ may join to form asubstituted or unsubstituted, saturated, partially unsaturated oraromatic, cyclic or polycyclic substituent.
 36. The compound of claim 31wherein Y is present and is selected from CH₂, CH₂CH₂, CH(CH₃)₂, SiMe₂,SiPh₂, SiMePh, Si(CH₂)₃, and Si(CH₂)₄, O, S, NMe, NPh, PMe, PPh, whereMe is methyl and Ph is phenyl.
 37. A metallocene compound represented bythe formula (3):

wherein M is a group 3, 4, 5 or 6 transition metal atom, or a lanthanidemetal atom, or actinide metal atom; R^(1′), R^(2′), R^(3′), R^(4′),R^(5′), R^(6′), R^(7′) and R^(8′) are, independently, hydrogen, or ahydrocarbyl, substituted hydrocarbyl, halogen, halocarbyl, substitutedhalocarbyl, silylcarbyl, substituted silylcarbyl, germylcarbyl,substituted germylcarbyl, or other heteroatom substituents wherein theheteroatom is bonded directly to a ring carbon atom of the fluorenylligand and is boron, a Group 14 atom that is not carbon, a Group 15atom, or a Group 16 atom, and adjacent R^(1′), R^(2′), R^(3′), R^(4′),R^(5′), R^(6′), R^(7′) and R^(8′) may be joined together to form asubstituted or unsubstituted, saturated, partially unsaturated, oraromatic cyclic or polycyclic substituent; R^(9′) is a halogensubstituent; Y is an optional bridging group that contains a Group 13,14, 15, or 16 element, and that is bonded to A and to any singlebondable position of the fluorenyl ligand, and is present when y is oneand absent when y is zero, and when present, Y replaces one of R^(1′),R^(2′), R^(3′), R^(4′), R^(5′), R^(6′), R^(7′) and R^(8′) in formula(3); y is zero or one; A is a substituted or unsubstitutedcyclopentadienyl ligand, a substituted or unsubstituted indenyl ligand,or a substituted or unsubstituted fluorenyl ligand; and each X is aunivalent anionic ligand, or two X are joined and bound to the metalatom to form a metallocycle ring, or two X are joined to form achelating ligand, a diene ligand, or an alkylidene ligand.
 38. Themetallocene compound of claim 37 wherein said halogen substituent is achloro, bromo, or iodo substituent.
 39. The metallocene compound ofclaim 37 wherein said halogen substituent is a chloro or bromosubstituent.
 40. The compound of claim 37 wherein Y is present and is abridging group containing boron or a Group 14, 15 or 16 element.
 41. Thecompound of claim 37 wherein Y is present and is selected from the groupconsisting of: S, O, NR′, PR′, AsR′, SbR′, O—O, S—S, R′N—NR′, R′P—PR′,O—S, O—NR′, O—PR′, S—NR′, S—PR′, R′N—PR′, R′₂C, R′₂Si, R′₂Ge, R′₂CCR′₂,R′₂CCR′₂CR′₂, R′₂CCR′₂CR′₂CR′₂, R′C═CR′, R′C═CR′CR′₂, R′₂CCR′═CR′CR′₂,R′C═CR′CR′═CR′, R′C═CR′CR′₂CR′₂, R′₂CSiR′₂, R′₂SiSiR′₂, R′₂CSiR′₂CR′₂,R′₂SiCR′₂SiR′₂, R′C═CR′SiR′₂, R′₂CGeR′₂, R′₂GeGeR′₂, R′₂CGeR′₂CR′₂,R′₂GeCR′₂GeR′₂, R′₂SiGeR′₂, R′C═CR′GeR′₂, R′B, R′₂C—BR′, R′₂C—BR′—CR′₂,R′₂C—O—CR′₂, R′₂CR′₂C—O—CR′₂CR′₂, R′₂C—O—CR′₂CR′₂, R′₂C—O—CR′═CR′,R′₂C—S—CR′₂, R′₂CR′₂C—S—CR′₂CR′₂, R′₂C—S—CR′₂CR′₂, R′₂C—S—CR′═CR′,R′₂C—Se—CR′₂, R′₂CR′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR′₂CR′₂, R′₂C—Se—CR′═CR′,R′₂C—N═CR′, R′₂C—NR′—CR′₂, R′₂C—NR′—CR′₂CR′₂, R′₂C—NR′—CR′═CR′,R′₂CR′₂C—NR′—CR′₂CR′₂, R′₂C—P═CR′, and R′₂C—PR′—CR′₂ where R′ ishydrogen or a C₁-C₂₀ containing hydrocarbyl, substituted hydrocarbyl,halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbylsubstituent and optionally two or more adjacent R′ may join to form asubstituted or unsubstituted, saturated, partially unsaturated oraromatic, cyclic or polycyclic substituent.
 42. The compound of claim 37wherein Y is present and is selected from CH₂, CH₂CH₂, CH(CH₃)₂, SiMe₂,SiPh₂, SiMePh, Si(CH₂)₃, and Si(CH₂)₄, O, S, NMe, NPh, PMe, PPh, whereMe is methyl and Ph is phenyl.
 43. A metallocene compound selected from:bis(η⁵-2-bromo-indenyl)zirconium dichloride,(η⁵-2-bromoindenyl)zirconium tribromide,(η⁵-2-bromoindenyl)(η⁵-2-mesityl-indenyl)zirconium dibromide,(η⁵-2-bromoindenyl)(η⁵-2-pyrrolidinyl-indenyl)zirconium dibromide,(η⁵-2-bromoindenyl)(η⁵-2-(3,5-dibromophenyl)-indenyl)zirconiumdibromide, (η⁵-2-bromoindenyl)(η⁵-2-phenylindenyl)zirconium dibromide,and bis(η⁵-2-bromo-4,7-dimethyl-indenyl)zirconium dichloride.
 44. Acatalyst system comprising the metallocene compound of claim 1 and anactivator.
 45. A process for polymerizing olefins comprising contactingthe catalyst system of claim 44 with at least one olefin.
 46. Theprocess of claim 45 wherein said at least one olefin comprises ethyleneand/or propylene.
 47. A catalyst system comprising the metallocenecompound of claim 3 and an activator.
 48. A process for polymerizingolefins comprising contacting the catalyst system of claim 47 with atleast one olefin.
 49. The process of claim 48 wherein said at least oneolefin comprises ethylene and/or propylene.
 50. A catalyst systemcomprising the metallocene compound of claim 11 and an activator.
 51. Aprocess for polymerizing olefins comprising contacting the catalystsystem of claim 50 with at least one olefin.
 52. The process of claim 51wherein said at least one olefin comprises ethylene and/or propylene.53. A catalyst system comprising the metallocene compound of claim 19and an activator.
 54. A process for polymerizing olefins comprisingcontacting the catalyst system of claim 53 with at least one olefin. 55.The process of claim 54 wherein said at least one olefin comprisesethylene and/or propylene.
 56. A catalyst system comprising themetallocene compound of claim 31 and an activator.
 57. A process forpolymerizing olefins comprising contacting the catalyst system of claim56 with at least one olefin.
 58. The process of claim 57 wherein said atleast one olefin comprises ethylene and/or propylene.
 59. A catalystsystem comprising the metallocene compound of claim 37 and an activator.60. A process for polymerizing olefins comprising contacting thecatalyst system of claim 59 with at least one olefin.
 61. The process ofclaim 60 wherein said at least one olefin comprises ethylene and/orpropylene.
 62. A catalyst system comprising the metallocene compound ofclaim 43 and an activator.
 63. A process for polymerizing olefinscomprising contacting the catalyst system of claim 62 with at least oneolefin.
 64. The process of claim 63 wherein said at least one olefincomprises ethylene and/or propylene.